ES2382652T3 - Electrochromic polymers and polymeric electrochromic devices - Google Patents

Abstract

The subject invention pertains to electrochromic polymers and polymer electrochromic devices. In a specific embodiment, two complementary polymers can be matched and incorporated into dual polymer electrochromic devices. The anodically coloring polymers in accordance with the subject invention can allow control over the color, brightness, and environmental stability of an electrochromic window. In addition, high device contrast ratios, high transmittance changes, and high luminance changes can be achieved, along with half-second switching times for full color change. Also provided are electrochromic devices such as advertising signage, video monitors, stadium scoreboards, computers, announcement boards, warning systems for cell phones, warning/information systems for automobiles, greeting cards, electrochromic windows, billboards, electronic books, and electrical wiring. The subject invention also provides for the use of complementary electrochromic polymers in the manufacture of electrochromic devices. In some embodiments, the devices of the invention can be prepared using metal vapor deposition or line patterning.

Description

Electrochromic polymers and polymeric electrochromic devices

The reference invention was carried out with government aid within the framework of a research project supported by the Office of Scientific Research / PKS of the Air Forces (No. 49620-00-1-0047); the Army Research Office (No. DAAD 19-00-1-002); the National Science Foundation (No. CHE9629854); and the Office of Naval Research (No. N000014-00-1-0164).

Background of the invention

There are numerous procedures responsible for modulating visible light. Among them, electrochromic techniques can use the reversible change in color and / or optical density obtained by a redox process in which the oxidized and reduced forms have different colors, refractive indices or optical densities. These techniques are easily used in many applications such as display panels (1), camouflage materials (2), variable reflectance mirrors (3), variable optical attenuators and variable transmittance windows (4, 5, 6). For example, the Gentex electrochromic mirror system has been successfully marketed in the car industry.

Electrochromic devices (ECD) based on inorganic semiconductors have a long history, and their performance has continuously improved since their creation (7). When viewed in this context, the recent rapid progress made with conductive and electroactive organic polymers in a variety of fields suggests that they can find numerous practical applications in the short term (8). These materials have made important contributions to the emerging fields of electrochromic devices (4), as well as organic light emitting diodes (9, 10) and photovoltaic materials (11). In terms of electrochromic materials, the remarkable advances in their performance can be analyzed from various fronts. First, the range of colors currently available effectively covers the entire visible spectrum (12) and also extends across the microwave, near infrared and mid infrared regions. This is due to the ability to synthesize a wide variety of polymers with varying degrees of conjugation and electron-rich character. For example, a good adjustment of the band gap and, consequently, of the color is possible, through the modification of the polymer structure by functionalization of monomers (13), copolymerization (14) and the use of mixtures, laminates and compounds (15,16). Second, there is the notable increase in the useful lives of the devices. The key to this is the control of degradation processes within polymeric materials (by reducing the occurrence of structural defects during polymerization) and the redox system (17,18). Third, polymer-based ECDs have achieved extremely rapid change times (milliseconds) for large changes in optical density. This rapid change is attributed to a very open morphology of electroactive films, allowing rapid transport of doping ions (19). Other beneficial properties of polymers are the outstanding coloring efficiencies (20) along with their general processability.

US5995273 discloses a dual electrochromic device comprising between two electrodes a layer of poly (3-alkylthiophene), a gel electrolyte and another poly (3-alkylthiophene).

US5446577 discloses an electrochromic device comprising between two electrodes a layer of polyaniline, an electrolyte, the second electrode is covered with polyaniline.

S. A. Sapp et al. report in Chemistry of Materials, vol. 10, November 7, 1998, pages 2101-2108, of a dual polymer electrochromic device with cathodic coloration polymers, such as derivatives of EDOT polymers, and anodic coloration polymers, such as derivatives BEDOT-NCH3Cz and BEDOT-BP.

Brief description of the figures

Figure 1. The superposition of the UV-Vis-IRC spectra of individual polymer films deposited on ITO / glass substrates. Figure 1A represents the polymer absorption states in which PProDOP-NPrS is in the oxidized form and PProDOT-Me2 is in the neutral form. The sum of the two absorption spectra (dashed line) represents the most likely behavior of the colored state of a device based on these two polymers. Figure 1B represents the discolored state of the polymer films. The sum of the spectra of the neutral PProDOP-NPrS and the doped PProDOT-Me2 (dashed line) provides a high contrast with the colored state in the entire visible region, generating a highly transmitting device. For clarification purposes, the visible region of the spectrum (400-800 nm) is marked with vertical dashed lines. All experiments were carried out using a Varian Carry 5E spectrophotometer. The polymers were changed in a specially designed three electrode electrochemical spectrum cell.

Figure 2. Transmittance spectra and photographs of devices using PProDOT-Me2 as the cathodic coloration polymer and PBEDOT-NMeCz (A) and PProDOP-NPrS (B) as the anode coloration layers with the devices in the two extreme states ( colored and discolored). The dashed vertical line represents the beginning of the cut of the neutral PBEDOT-NMeCz.

Figure 3A Transmittance as a function of the changeover time of (a) a PProDOT-Me2 / PBEDOTNMeCz device, (b) a PProDOT-Me2 / PProDOP-NPrS device and (c) a PProDOT-Me2 film. In these experiments, the variation of monochromatic light transmitted to Ammax during repeated redox change experiments was monitored. All experiments were carried out on a Varian Carry 5E spectrophotometer. The thickness of the PProDOT-Me2 layer was 200 nm, measured using a DekTak Sloan 3030 profilometer. Figure 3B shows the xy trajectory of the hue and saturation for the device and, as the applied potential changes from - 2.5 V to + 1.5V, a straight line is observed that extends between a dark blue zone of the color space to a highly transmitting blue-green color (near the white point).

Figure 4A Luminance analysis of a PProDOT-Me2 / PProDOP-NPrS device. The potential dependence of the relative luminance was monitored using a white light source of D50. Figure 3B shows the life of the PProDOT-Me2 / PProDOP-NPrS device for multiple electrochromic changes. This study was carried out by continuously increasing the device voltage between -1 and +1 V with a delay of 30 s at each potential, allowing a total color change and a retention period. During this time, the luminance was monitored over a period of 7 days. The upper line (_) shows the decrease in the luminance of the device in the discolored state with the number of cycles performed, while the lower line (e) is the fading of the dark state during continuous change. All measurements were carried out with a CS 100 Minolta chromometer.

Figure 5. Schematic representation of a transmitter type EDC. It consists of two thin polymer films deposited on a glass coated with transparent tin and indium oxide (ITO) and separated by a viscous gel electrolyte based on LiN (CF3SO2) 2 dissolved in a swollen poly (methyl methacrylate) matrix with acetonitrile / propylene carbonate. The construction of the device is carried out with an oxidatively doped polymer, while the other is neutral, and both films are simultaneously in their transmitter or absorption states. Thus, the device is observed as discolored or colored. The application of a voltage neutralizes the doped polymer with the concomitant oxidation of the complementary polymer, inducing color formation or discoloration. The PProDOT-Me2 changes from a light blue highly transmitting in the doped state to a dark blue-purple in the neutral state, while the PProDOP-NPrS changes from a gray-green state to an almost transparent neutral state. The color representations shown are determined color coordinates L * a * b *.

Figure 6. Synthesis of N-substituted ProDOP

Figure 7. Electrodeposition of N-alkyl ProDOP by potential scanning from a 0.01 M solution of monomer in 0.1 M LiClO4 / PC at 20 mV / s on a Pt button (area = 0.02 cm2) : (a) N-Me PProDOP (20 cycles), (b) N-Pr PProDOP (150 cycles), (c) N-Oct PProDOP (150 cycles), (d) N-Gly PProDOP (50 cycles).

Figure 8. Cyclic voltamogram of thin films of N-alkyl PProDOP in solution without 0.1 M monomer of LiClO4 / PC: (A) N-Me PProDOP, (B) N-Pr PProDOP, (C) N-Oct PProDOP, (D) N-Gly PProDOP at a scan rate of (a) 50 mV / s, (b) 100 mV / s, (c) 150 mV / s, (d) 200 mV / s.

Figure 9. Dependence of the scanning speed of the N-Pr PProDOP film in solution without 0.1 M monomer of LiClO4 / PC: (A) change in the anodic and cathodic peak currents with the scanning speed, (B ) peak separation (LEp) with increasing scan speed.

Figure 10. N-alkyl PProDOP spectrum electrochemical in 0.1 M LiClO4 / PC vs. Fc / Fc +: (A) N-Me PProDOP to applied potentials of: (a) -500 mV, (b) -400 mV, ( c) -300 mV, (d) -275 mV, (e) -250 mV, (f) -230 mV, (g) -200 mV,

(h)

 -160 mV, (i) -120 mV, (j) -75 mV, (k) 0 mV, (1) +100 mV, (m) +300 mV, (n) +500 mV, (o) +700 mV; (B) N-Pr PProDOP to applied potentials of: (a) -400 mV, (b) -300 mV, (c) -200 mV, (d) -150 mV, (e) -100 mV, (f) -80 mV,

(g)

 -60 mV, (h) -40 mV, (i) -20 mV, (j) 0 mV, (k) +50 mV, (1) +100 mV, (m) +200 mV, (n) +400 mV, (o) +600 mV; (C) N-Gly PProDOP to applied potentials of (a) -200 mV, (b) -70 mV, (c) -60mV, (d) -50 mV, (e) -40 mV, (f) -30 mV,

(g)

 -20 mV, (h) -10 mV, (i) 0 mV, (j) +20 mV, (k) +60 mV, (1) +200 mV, (m) +300 mV, (n) +400 mV, (o) +700 mV.

Figure 11. N-Gly PProDOP transmittance in the visible region as a function of wavelength (nm) for 3 different oxidation states: (a) neutral, (b) intermediate, (c) doped.

Figure 12. Colorimetry (x-y diagram) of (A) N-Me PProDOP and (B) N-Gly PProDOP

Figure 13. Relative luminance of N-Me PProDOP (0) and N-Gly PProDOP (e) calculated from Yxy coordinates as a function of the potential applied against Fc / Fc +

Figure 14 illustrates (schematically) a sandwich structure of an outwardly active electrode device originally described in the patent literature [R. B. Bennett, W. E. Kokonasky, M., J. Hannan,

L. G. Boxall, US Pat. UU. 5,446,577, 1995; b) P. Chandrasekhar, US Pat. UU. 5,995,273, 1999].

Figure 15. Dermatized ProDOP chemical structures.

Figure 16. Cyclic voltammetric electrodeposition of ProDOP-BuOH on a Pt button electrode at 20 mV / s. The inner graph shows the irreversible oxidation of the monomer and the nucleation loop of the first scan.

Figure 17 represents the initial set of prepared 3,4-alkylenedioxypyrrole monomers.

Figure 18 represents the general synthetic route for 3,4-alkylenedioxypropyls.

Figure 19 shows N-alkylated ProDOP with a variety of side substituents ranging from simple alkyl groups to derivatives of glyme, alcohol of glyme and sulfonatealkoxy.

Figure 20 illustrates iodo-decarboxylation in N-benzyl-3,4-ethylenedioxypyrrol-2,5-dicarboxylic acid (13).

Figure 21 illustrates that EDOP benzyl protection was carried out satisfactorily with a 90% yield to provide N-benzyl-EDOP (17).

Figure 22 illustrates the synthesis process of EDOT, EDOP and thiophene combined: cyanovinylene donor and acceptor monomers.

Figure 23 illustrates the design and synthesis of a dioxypyrrole derivatized with a 14-crown-4-ether.

Figure 24 provides a scheme for the synthesis of a series of modified ProDOP monomers having alkyl chains attached to the central methylene of the propylenedioxy moiety.

Figures 25A-B depict ECD transmitters and reflectors that can use electrochromic polymers of the reference invention (Old Figures 34-35).

Figure 26. Synthesis of N-substituted ProDOP

Figure 27. Electrodeposition of N-alkyl ProDOP by potential scanning from a 0.01 M solution of monomer in 0.1 M LiClO4 / PC at 20 mV / s on a Pt button (area = 0.02 cm2) : (A) N-Me PProDOP (20 cycles), (B) N-Pr PProDOP (150 cycles), (C) N-Oct PProDOP (150 cycles), (D) N-Gly PProDOP (50 cycles), ( E) N-PrS PProDOP (15 cycles).

Figure 28. Cyclic voltamograms of thin films of N-alkyl PProDOP in solution without 0.1 M monomer of LiClO4 / PC: (A) N-Me PProDOP, (B) N-Pr PProDOP, (C) N-Oct PProDOP, (D) N-Gly PProDOP, (E) N-PrS PProDOP at a scan rate of (a) 50 mV / s, (b) 100 mV / s, (c) 150 mV / s, (d) 200 mV / s.

Figure 29. Cyclic voltamogram of a thin film of N-PrS PProDOP in solution without 0.1 M monomer of LiClO4 / PC. The polymer film was galvanically grown at a current density of 0.04 mA / cm2 by passing a total charge of 10 mC / cm2 from a 0.01 M monomer in PC: H2O (94: 6) without electrolyte support. The scan speeds are (a) 20 mV / s, (b) 50 mV / s, (c) 100 mV / s, (d) 150 mV / s, (e) 200 mV / s.

Figure 30. (A) Variation of the anodic and cathodic peak currents as a function of the scan rate for an N-PrS PProDOP film in a 0.1 M solution of LiClO4 / CAN; (B) Variation of the anodic (�) and cathodic (0) peak currents as a function of the number of cycles for a 0.12 μm thick film of N-PrS PProDOP, cycled 10,000 times at a scanning speed of 100 mV / s

Figure 31. N-alkyl PProDOP spectrum electrochemical in 0.1 M LiClO4 / PC vs. Fc / Fc +: (A) N-Me PProDOP to applied potentials of: (a) -500 mV, (b) -400 mV, ( c) -300 mV, (d) -275 mV, (e) -250 mV, (f) -230 mV, (g) -200 mV,

(h)

 -160 mV, (i) -120 mV, (j) -75 mV, (k) 0 mV, (1) +100 mV, (m) +300 mV, (n) +500 mV, (o) +700 mV; (B) N-Pr PProDOP to applied potentials of: (a) -400 mV, (b) -300 mV, (c) -200 mV, (d) -150 mV, (e) -100 mV, (f) -80 mV,

(g)

 -60 mV, (h) -40 mV, (i) -20 mV, (j) 0 mV, (k) +50 mV, (1) +100 mV, (m) +200 mV, (n) +400 mV, (o) +600 mV; (C) N-Gly PProDOP to applied potentials of (a) -200 mV, (b) -70 mV, (c) -60mV, (d) -50 mV, (e) -40 mV, (f) -30 mV,

(g)

 -20 mV, (h) -10 mV, (i) 0 mV, (j) +20 mV, (k) +60 mV, (1) +200 mV, (m) +300 mV, (n) +400 mV, (o) +700 mV; (D) N-PrS PProDOP to applied potentials of a) -0.40 V, (b) -0.30 V, (c) -0.25 V, (d) -0.20 V, (e) -0.15 V, (f) -0.10 V, (g) -0.05 V, (h) 0.00 V, (i) +0.05 V, (j) +0.10 V, (k) +0.15 V, (1) +0.20 V, (m) +0.25 V, (n) +0.30 V, (o) +0.40 V, (p) +0.50

V.

Figure 32. N-Gly PProDOP transmittance in the visible region as a function of wavelength (nm) for 3 different oxidation states: (a) neutral, (b) low doping level, (c) high level of doping

Figure 33. Colorimetry (x-y diagram) of (A) N-Me PProDOP and (B) N-Gly PProDOP and (C) N-PrS PProDOP

Figure 34. Relative luminance of N-Me PProDOP (0) and N-Gly PProDOP (e) as a function of the potential applied against Fc / Fc +.

Figures 35A-F: Manufacture of ECD modeled by metallic vapor deposition (MVD).

(A-C) Design of the masks used to model metal on a flat surface. Left: 2x1 pixels. Center: 2x2 pixels. Right: 3x3 pixels.

(D)

 Schematic sample of an MVD procedure for coating surfaces with modeled metal electrodes.

(AND)

 Gold electrode modeled on a porous polycarbonate membrane. The image on the left (and its optical magnification - 40X) shows the gold spots (size of approximately 10 μm) deposited on a glass substrate through the pores. The center image shows the 2x2 mask used during this procedure. The image on the right shows the layer of gold deposited on the polycarbonate membrane. The optical magnification of the image indicates the porous nature of the gold electrode.

(F)

 Schematic cross-sectional view of an ECD construction with a porous membrane.

Figure 36: Photographs of PEDOT and PBEDOT-B (OC12H25) 2 potentiostatically reduced (left) and oxidized (right) in 0.1M TBAP / ACN electrolyte. The films were deposited on an ITO / glass electrode (1 cm2) using 20 mC deposition charge.

Figures 37A-B: Photograph of a 1 pixel device constructed in accordance with Figure 35F (D2) using PEDOT as an active surface layer and as a counter electrode.

(TO)

Colored and discolored states of change of the active surface layer.

(B)

Dependency of loading / unloading time during the exchange procedure.

Figure 38: Photographs of the electrochemical configuration of the 2x2 pixel device during the change in 0.1M TBAP / PC, showing a fully reflective to fully colored surface.

Figures 39A-C: PEDOT VC (39A), PBEDOT-B (OC12H25) 2 (39B) and the films together (39C) in 0.1M TBAP / PC at 100, 100 and 50 mV / s, respectively, for the movies of figure 38.

Figure 40: Load accumulation of the two films of Figure 38 in 0.1M TBAP / PC, showing the transition from discolored to colored as a function of time. Internal graphic: time dependence of the repetitive loading / unloading procedure under the same experimental conditions.

Figure 41: Schematic diagram of an interleaved transparency film substrate coated with Baytron P® The color shown in the scheme is the actual color of the coated films measured by a Minolta CS-100 colorimeter.

Figure 42: Schematic representation of the electrochromic change of a laterally modeled device between the transmitter and colored states. This device comprises two polymers on the same surface.

Figure 43: Percentage of transmittance (% T) of transparency film substrates with PEDOT coating, linearly modeled (S1 = one layer of PEDOT, S2 = two layers of PEDOT, S3 = three layers of PEDOT).

Figures 44A-B: Photographs of PEDOT EC deposited on an interdigitated PEDOT electrode modeled linearly. Figure 44A shows the electrochromic change of the PEDOT between its redox states. PEDOT area deposited ~ 3 cm2, deposition load ~ 14 mC / cm2. Figure 44B shows an optical micrograph of deposited PEDOT (center line) and non-deposited lines.

Figure 45: Change of color of PBEDOT-Cz on a Baytron P® coated electrode to various potentials based on L * a * b values recorded by a Minolta CS-100 colorimeter.

Figure 46: Photograph of the electrochromic change of PBEDOT-Cz in a TBAP electrolyte solution (0.1 M) / ACN on a linearly interdigitated electrode modeled from PEDOT.

Figure 47: Schematic illustration of a plastic substrate coated with ITO, interdigitated created with linear modeling.

Figure 48: Photograph demonstrating the electrochromic change of PEDOT on an interleaved transparency film substrate, coated with ITO.

Figures 49A-B: Interdigitated electrode designs for gold deposition without electric current.

Figures 50A-C: Optical micrographs of transparency films deposited with gold, interspersed by linear modeling. The modeled lines are shown under magnification (A) 10x, (B) 40X, and (C) 100x.

Figure 51: Photograph demonstrating the EC change of (PEDOT-PEDOT) in linearly modeled gold in a solid-state device with interdigitated electrodes (IDE).

Figure 52: Photograph demonstrating the EC change of a 2 pixel linearly modeled (PEDOT-PEDOT) gold device in a 0.1M LiClO4 / PC electrolyte solution.

Figures 54A-B: Figure 54A shows an optical micrograph of a vulcanized line on an ITO / glass substrate. The lateral resolution of the lines was determined to be 60 μm. Figure 54B shows the profile scan of a vulcanized line. The lines drawn on ITO / glass by this procedure resulted in the isolation of regions modeled by> 20 MO.

Figures 55A-B: Figure 55A is a UF design applied on an ITO / polyester substrate. Figure 55B depicts an electrochromic change of a UF device based on (P3MTh-P3MTh) in a 0.1 M solution of TBAP / ACN.

Figures 56A-56B: Schematic representation of a lateral interdigitated ECD. Figure 56A shows the independent electropolymerization on interdigitated fingers (I and II). Black areas represent non-conductive sites. The white areas are conductive. Figure 56B illustrates the EC change of the lateral device between its complementary redox and colored states.

Figures 57A-B: Polymer pairs showing a high contrast presentation (upper and lower left part) and color matching (upper and lower right part) using devices constructed with the same polarization (Figure 57A) and with opposite polarization (Figure 57B).

Figure 58A-58C: Photographs of gold modeled electrodes obtained by the linear modeling procedure (Figure 58A: 2x2 electrode, Figure 58B: 3x3 pixel electrode and Figure 58C: interdigitated electrode).

Brief description of the tables

Table 1. Oxidation potentials, ratio between the anodic and cathodic peak potentials (ipa / ipc), peak separation (LEp), maximum wavelength (Amáx) and band gap (Eg) of PProDOP.

Table 2. Colors observed at different levels of oxidation in N-Me PProDOP and N-Gly PProDOP with coordinates expressed in the color spaces L * a * b * CIE 1931 Yxy and CIE 1976.

Table 3: Specific electrochromic polymers.

Table 4: General electrochromic polymers.

Table 5: Exemplary complementary electrochromic polymers.

Table 6: Complementary EC polymers and exemplary colors.

Table 7: Complementary EC polymers and exemplary colors.

Table 8: General modeling procedures.

Brief Description of the Invention

In electrochromic materials, electrochemical oxidation or reduction induces a reversible change in reflected or transmitted light. Since its discovery in inorganic materials, 21 this capacity has aroused the interest of scientists during the last thirty years.22 The electrochromic properties have proven to be

windows26,27,28,29,30

especially useful or promising for the construction of mirrors, 23 screens, 24.25 and chameleon materials of earthy tones.31,32,33 Based on this concept, 34.35 rearview mirrors and electrochromic exterior mirrors have recently been marketed in the automotive industry .

Although the first electrochromic devices studied were produced using inorganic compounds such as tungsten trioxide (WO3) and iridium dioxide (IrO2), 36 organic compounds have proved interesting for electrochromic materials including: viologens, metaphthalocyanines and conductive polymers.37 They can observe different electronic spectra and, therefore, different colors, during the change of these compounds between their different redox states. The possibility of combining a lower processing cost with an enhanced electrochromic rate of change and contrast has focused the interest of scientists on the use of conductive polymers.38,39 In fact, the extended delocalization of electrons along the skeleton of the polymer (in the neutral state) results in an optical absorption band (transition nn *) in the visible region of the electromagnetic spectrum. A redox process (oxidation or reduction) will generate charge transporters in the conjugated skeleton, which leads, respectively, to the insertion of an anion or a cation. Conductive polymers have several advantages over inorganic compounds as electrochromic materials. First, there are its outstanding coloring efficiency and rapid changeability, as shown by poly (3,4-alkylenedioxythiophene) derivatives (PXDOT) .40,41 The second is the ability to produce multiple colors with the same material.33 Finally, it is possible to make a fine adjustment of the band gap and, therefore, of the color, through the modification of the chemical structure of the polymer.33,42,43 This list of the advantages of conductive polymers over materials inorganic would not be complete without mentioning that, if polymers are obtained

Detailed description of the invention

A specific embodiment of a transmitter type electrochromic material is schematically shown in Figure 5. The pairing of the number of redox sites in each film can enhance the contrast of a device, since the absorption and transmission ends can be achieved.

A cathodic coloration polymer can be defined as one that passes from an almost transparent state to a highly colored state after charge neutralization (reduction) of the p-doped form, while an anodic coloration polymer can be defined as that which is highly transmitter neutral and absorbs in the oxidatively doped state.

The reference devices can incorporate conductive polymers based on poly (3,4-ethylenedioxythiophene) (PEDOT) and their derivatives, which can show high electrochromic contrasts, low oxidation potentials, high conductivity, as well as good electrochemical and thermal stability (13 ). For example, substituted poly (3,4-propylenedioxythiophene) dimethyl (PProDOT-Me2) can be used as a cathodic coloring polymer for use in the electrochromic reference devices. Advantageously, the PProDOT-Me2 shows a high contrast in the visible region: approximately 78% at Ammax (580 nm) and a luminance change of approximately 60% measured by colorimetry. This high contrast at 580 nm corresponds to a wavelength at which the human eye is highly sensitive, changing the polymer from a light blue highly transmitting in the doped state to a dark blue-purple in the neutral state. Consequently, PProDOT-Me2 can be incorporated into a variable reflectance ECD that shows an extraordinarily high contrast across the visible, IRC and middle IR regions of the electromagnetic spectrum. In a specific embodiment, such a device can allow thousands to hundreds of thousands of deep double cycles with little loss of contrast.

An anodic coloring polymer having a band gap (Eg)> 3.0 eV (beginning of the transition n to n * at <410 nm) can be chosen with all absorption falling into the ultraviolet region of the spectrum. In addition to the complementary optical properties, preferred ECD operation may include a high degree of electrochemical reversibility and compatibility. Many polymers conjugated with high gaps (for example poly (phenylene vinyl) (PPV), poly (p-phenylene) (PPE), etc.) have high oxidation potentials. In a specific embodiment, the reference invention relates to electrochemically easily polymerized monomers that can provide polymers that have EC properties complementary to the cathodic coloration PProDOT-Me2, so that an ECD is achieved that can undergo a different change from a highly transmitting state to a deeply absorbing state.

Several polymers of anodic coloration based on carbazole, biphenyl and other aromatic units linked through electropolymerizable EDOT moieties (44, 45) have been synthesized. Although the ECDs incorporating these types of polymers showed coloration efficiencies, lifetimes and prominent change times (18, 19), the band gaps of the anodic coloration polymers are not high enough to exclude the nn * absorption of the visible region, providing a coloration to the transmitting state of the devices. The reference invention relates to the synthesis and electropolymerization and redox exchange properties of a new series of conductive polymers based on 3,4-alkylenedioxypropyls and 3,4-alkylenedioxythiophenes. As the pyrroles have relatively high LUMO levels, the band gaps for PEDOP (2.0 eV) and the propylene bridge analog (PProDOP, 2.2 eV) are greater than their corresponding thiophene (PEDOT and PProDOT) which have band gaps of 1.61.7 eV.

The reference invention also relates to a series of N-substituted ProDOPs, which can raise the band gap of the dioxypyrrole polymers even further. In addition to the advantage of this high gap, these polymers can retain the electron-rich character of the PXDOP family, allowing their electrosynthesis and change under mild conditions. The polymerization can be forced through positions 2 and 5 as desired, resulting in a material with few structural defects and, consequently, better electrochemical cyclisation capacity, compared to the original polypyrrole. Finally, the substitution of N-alkyl inductively increases the electron density in the monomer, thus presenting a lower oxidation potential than the non-derivatized ProDOP. In a specific embodiment, the sulfonated N-propane PProDOP (PProDOP-NPrS) may allow the start of the n-n * transition to be at the limit of the visible and ultraviolet regions of the spectrum (Eg> 3.0 eV). Thus, the electronic absorption is transferred to UV and the polymer is colorless in the neutral state. In addition, the PProDOP-NPrS has a relatively fast deposition rate and good film quality, together with the achievement of a colored doping state.

The reference invention can achieve a high contrast in dual polymer ECD by matching the anodic and cathodic properties in order to obtain a neutral, highly transmitting color window, in one state, which shows low absorption throughout the visible region. After changing a small polarized potential (approx. 1.0 V) the window can be converted to a relatively dark relatively colored state. Figures 1A and 1B demonstrate this by superimposing the UV-visible spectra of the individual polymers in their doped and neutral states. Figure 1A represents the absorption state in which the PProDOP-NPrS is in the oxidized state and the PProDOT-Me2 is in the neutral form. The sum of the two absorption spectra represents the most likely behavior of the colored state of a device based on these two polymers. There are several factors that combine to reach a very saturated and broadband color absorbance window. First, the neutral PProDOT-Me2 has its absorption in the center of the visible region (Amáx = 580 nm), where the human eye is more sensitive. In addition, the vibrational separation of the HOMO-LUMO transition widens the absorption peak along a larger area of the visible spectrum. The absorption of oxidatively doped PProDOP-NPrS begins at 500 nm and its absorbance increases in the IRC region, where the contribution of PProDOT-Me2 is small. The discolored state of the device and polymer films is depicted in Figure 1B. The sum of the spectra of the neutral PProDOP-NPrS and the doped PProDOT-Me2 provides a high contrast with the colored state in the entire visible region, generating a highly transmitting device.

Figures 2A and 2B show the transmittance spectra and photographs of devices according to the reference invention using PProDOT-Me2 as the cathodic coloration polymer and poly [3,6-bis (2-ethylenedioxythienyl) -N-methyl-carbazole] ( PBEDOT-NMeCz) (device A) and PProDOP-NPrS (device B, respectively) as the layers of anodic coloration with the devices in the two extreme states (colored and discolored). Both devices switch between the two forms when a bias voltage of approximately ± 1.0 to 1.2 V is applied. By selecting intermediate bias voltages, the devices can continuously change from colored to transmitters and the spectra evolve from one end to the other. . The comparison of the results shows that the use of PProDOP-NPrS as the high band hollow polymer has several advantages over its corresponding carbazole. The main benefit is the opening of the transmission window along the entire visible spectrum by moving the n-n * transition to the ultraviolet region. The cut of the PBEDOT-NMeCz is evident at approx. 500 nm Another advantage of device B based on PProDOP-NPrS is the notable increase in optical contrast, as evidenced by the increase in L% T from 56% to 68% measured at 580 nm. In addition, while the PBEDOT-NMeCz is blue and the absorption of its load conveyor is at the same energy as the nn * transition of the gap absorption of the PProDOT-Me2 low, the PProDOP-NPrS is gray-green in the state oxidized, thus providing some additional blocking of the transmission of the opaque device in the region of 400-500 nm.

Normally, an important characteristic of an ECD is the response time required to make a change from transmitter to opaque and vice versa. In order to analyze the change characteristics of these windows, the variation of the monochromatic light at the maximum contrast wavelength was monitored during repeated increasing redox experiments. For a comparison, the change in the transmittance of a single PProDOT-Me2 film of the same thickness (approximately 200 nm) as the films used in the devices was monitored. As seen in Figure 3, both devices change quite quickly. The PProDOT-Me2 film alone can be changed effectively in approximately 0.5 s to reach 95% of its total transmission change (% LT = 76%). While device A changes by approximately 500 ms, device B has a somewhat larger dynamic range with a change in total transmission% in 600 ms. However, it should be noted that, by adding the PProDOP-NPrS layer, device B loses only 10% of the overall contrast compared to a single PProDOT-Me2 film.

Recently, colorimetric analysis (12) has been used to investigate the properties of electrochromic and light emitting polymers. Both luminance and x-y chromaticity diagrams provide valuable information to understand changes in the color and / or brightness of the devices. For example, the potential dependence of relative luminance offers a different perspective on the transmissivity of a material, since it refers to the perception of the human eye of transmittance across the visible spectrum as a function of doping in a single curve. Figure 3B shows the xy path of hue and saturation for device B as the applied potential is changed from -2.5 V to + 1.5V, which corresponds to the oxidative doping path of PProDOT-Me2 . A straight line is observed that extends between a dark blue zone of the color space and a blue-green one that is highly transmitting (near the white point). Therefore, the wavelength of the dominant color is the same throughout the entire fading procedure; the absorption decreases in intensity as represented by the reduction in color saturation. As seen in Figure 4A, in the discolored state, the window shows a luminance of 65% through the positive voltage values. A voltage of -0.5 V is required to induce a decrease in luminance; The luminance reduction of the device continues to increase until a potential of -2V is reached. The global luminance change, which is, in essence, the change in optical density perceived by the human eye, is 55%.

The stability of the discolored and / or colored states against multiple redox changes often limits the usefulness of electrochromic materials in ECD applications. The main causes of device failure are different electrochemical windows and / or environmental requirements of complementary materials. If the two EC materials have different electrochemical windows for their operation, then the applied voltage necessary to reach 100% of the optical contrast increases. Therefore, longer lifespans are expected for devices operating at low voltages, since high applied potentials can be detrimental to electrochromic films, electrolyte and even the ITO layer. In a specific embodiment, the oxidation process of the anodic material may coincide with the process of reduction of the EC cathodic material in order to maintain a load balance within the EDC.

Figure 4B shows the results of using colorimetry to monitor luminance change to investigate long-term stability for device B against multiple deep changes. The device loses 10% of its contrast during the first 500 cycles. After this conditioning period, degradation occurs extraordinarily slowly and the device loses only 4% of its luminance contrast over a period of 20,000 cycles of double potential. Since the devices are closed to environmental exposure, significantly longer lifespan can be realized.

5 Reference polymer dual ECDs can operate at low applied voltages (± 1.0 V), both films being compatible in the same electrochemical environment. This can greatly increase its lifespan, for example up to 86% retention of its initial color (96% retention after settlement) after 20,000 cycles. In addition, the PProDOP-NPrS has the ability to switch between a colorless neutral state and a doped gray-green state, having the rare property of being a true anodic colored polymer with

10 easily accessible redox change potentials. In addition, the doped PProDOP-NPrS widens the dark-state absorption peak of the ECD in both the 400-500 nm and the 700-800 nm region of the visible spectrum, where the contributions of the nn * transition of the film of PProDOT-Me2 are small. The complementary polymer based devices PProDOP-NPrS and PProDOT-Me2 can show an optical contrast of, for example, up to 70% at Ammax and a global luminance change of, for example, 53%. The

15 reference devices can change from a transparent state to a very dark, almost opaque state, in less than 1 second, which potentially converts them into useful polymer screens. These characteristics may allow the reference devices to achieve control over the color, brightness and environmental stability of an electrochromic window.

The reference invention provides electrochromic polymers comprising compounds as described in formula I and / or formula II.

Formula I Formula II

wherein X, Y and Z may be the same or different and are selected from the group consisting of S, N, O, Si (R8) 2, N-R7 and P-R7;

A1, A2 and A3 may be the same or different and are selected from the group consisting of S, N, O, Si (R8) 2, N-R7 and P-R7;

m is an integer between 0 and 10, preferably between 0 and 5, and more preferably between 0 and 3;

from R1 to R6 and R8 may not be, be the same or different and may be a moiety selected from the group consisting of one or two bond (s), H, alkyl, CN, OH, COOH, SOR7, SO2R7, SO3R7, heteroalkyl , alkenyl, alkynyl, arylalkyl, heteroaryl-alkynyl, aryl, aryl-alkyl, aryl-alkenyl, heteroaryl, heteroaryl-alkyl, heteroaryl-alkenyl,

30 cycloalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, cycloalkyl-alkyl,

R7 is a moiety selected from the group consisting of H, alkyl, aryl, COOH, heteroalkyl, alkenyl, alkynyl, arylalkyl, heteroaryl-alkyl, aryl, aryl-alkyl, aryl-alkenyl, heteroaryl, heteroaryl-alkyl, heteroaryl-alkenyl, cycloalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, cycloalkyl-alkyl;

n is at least about (or at least) three, preferably at least about (or at least) four, 35 and more preferably at least about (or at least) five; Y

In some embodiments, Z is Si and R8 is an alkyl, aryl or heteroaryl. Further embodiments provide polymers in which there are double or triple bonds between one or more of the following clusters of adjacent adjacent atoms: X and A1; A1 and A2 (when m = 1); each of (A2) m and (A2) m + 1 where m = 1, 2, 3, 4, 5, 6, 7, 8 or 9; A2 and A3, when m = 1; or A1 and A3 when A2 is not (m = 0). As would be apparent to those skilled in the art, when there are double or triple bonds between adjacent atoms illustrated in formulas I and II (for example, X and A1; A1 and A2 (when m = 1); each of (A2 ) my (A2) m + 1 when m = 1, 2, 3, 4, 5, 6, 7, 8 or 9; A2 and A3, when m = 1;

or A1 and A3 when A2 is not (m = 0)), R1, R2, R3, R4, R5 and R6 can, independently, be present, not be, be the same or different determined by the number of links, located in each corresponding position, which can form the atom.

Monomers for incorporation into electrochromic polymers according to the reference invention can be manufactured using, for example, Williamson's double esterification, transesterification or Mitsunobu reactions. Other reactions known to those skilled in the art may also be used for the preparation of monomers suitable for incorporation into electrochromic polymers of the invention.

The electrochromic polymers of the reference invention are electrical conductors and can be used in a variety of electrical devices as current conductors. Thus, the electrochromic polymers of the invention provide changing electrical devices comprising electrochromic polymers of the reference invention in which conductivity can be activated and deactivated. Non-limiting examples of such electrical conductors include circuits in microprocessors, electrical networks, power supply systems in buildings, lighting fixtures (as well as the electrical conductor) or as "wiring" in any electrical device. As another non-limiting example, the electrochromic polymers of the reference invention can be used as electroactive material contained within a translucent or transparent insulator. In such an invention, the polymer will be transparent (transmitter) in one state or the other. After applying a potential to a contact wire, the electrochromic polymer changes color, indicating that the circuit is energized. Alternative uses for such wiring include decorative lighting (the coloration of which is determined by the polymer used in the construction of the cable). Electrochromic polymers can be used in electrochromic devices such as variable optical attenuators for near infrared and visible light (for example, in telecommunication devices), microwave shutters for antennas (e.g. stealth technology), ECD warning signaling Pixels, e-books, video monitors, stadium markers or ad panels, video signage, camouflage, mobile phone alert systems, computers (e.g. personal digital assistants), electrochromic windows, greeting cards, dynamic murals and billboards. Therefore, the reference invention provides methods and means for the communication of information or artistic elements to individuals comprising the presentation of information or artistic elements to an individual through electrochromic screens. In such inventions, the information or artistic element is introduced into an electrochromic device and presented.

The reference invention uses electrochromic polymers of the invention and electrode modeling on substrate surfaces. For example, gold can be modeled on membranes using metal vapor deposition (MVD) techniques. Despite the large surface area, electrodes suitable for use in the present invention (as large as many square meters), electrochromic devices having a change of less than one second can be provided. The electrodes can also have a relatively small size. Various methods for manufacturing structured electrodes with various resolutions are well known in the art (see, for example, Holdcroft S. Adv. Mater. 2001 73: 1753; Schlultze JW; Morgenstem T .; Schattka D .; Winkels S. Electrochim. Minutes 1999, 44: 1847; and table 8). These modeling procedures are also useful for the construction of dual polymer flat devices, resulting in a new type of surface active electrochromic devices.

In another embodiment, it is possible to use electrodes modeled using simple and cheap methods such as linear modeling (LP) (see, for example, MacDiarmid et al. [2001] Synth. Met. 121: 1327) and ITO (oxide oxide) tin and indium) (Hohnholz et al. [1999] Adv. Mater. 11: 646). Linear modeling allows selective coating of substrates such as glass and transparency paper under normal atmospheric conditions as opposed to other high-cost modeling techniques such as lithography or vapor deposition. ITO vulcanization procedures allow the selective removal of ITO from the substrate with a metal tip in a closed circuit, followed by the deposition of polymer films on the electrodes formed by ITO vulcanization.

Lateral electrode modeling allows electrochemical deposition of two polymers on the same surface. These interdigitated electrode fingers (shown, for example, in Figures 41, 44A, 44B and 46) can be addressed individually. An electrochromic device comprising a cathodic coloration polymer and a complementary anodic coloration polymer can be deposited separately on the patterned lines. These polymers are then switched between their redox states and the device switches between their transmitter and colored states.

The reference invention also provides various electrochromic polymers useful in the construction of such ECDs comprising complementary electrochromic polymers and electrochromic screens or other electrochromic devices. Table 5 shows non-limiting possibilities to match a color or show a contrast between redox states in dual polymer EC devices (film 1 matches polymer 1, etc .; T indicates a transparent state; C1 is color 1, C2 is color 2, etc.). Tables 6 and 7 provide exemplary sets of complementary EC polymers. EC polymers suitable for use in EDC comprising complementary EC polymers include those described in Tables 3 and 4, as well as those derived from the set of polymers described therein (provided that the derivatives show the ability to change color when induced a change of redox state). The contrast or vividness of the color can be adapted by adjusting the thickness of the polymer coating of an electrode (for example, by adding additional layers of polymer film to the device).

Polymers that have a discolored state include PEDOT, PProDOT, PProDOT-Me2, PEDOP, PProDOP, PProDOP-NPS, PBEDOT-V, PProDOT-V, PProDOT, PBEDOT-Pyr and PBEDOT-B (OC12H25) 2. Polymers that have two or more colored states include, and are not limited to, P3MTh, PBEDOT-Fn, P3MTh, PBEDOT-BP, PBEDOT-C2 and P3BTh. Tables 3 and 4 define acronyms with the full names of polymers.

Both the LP and MVD procedures allow the construction of single-layer side ECDs in which the polymers on a surface are changed relative to each other and the power of the complementary electrochromism can be realized. Both transmitter and metal electrodes are modeled using the LP procedure. This procedure involves printing patterns on a substrate using a commercial printer, followed by coating the unprinted areas by a transparent, conductive PEDOT layer or a deposition without electric current from a conductor, such as gold. Subsequently, the ink is removed from the printer. Using this procedure, the modeling resolution is accessible, up to 30 micrometers (see, for example, Figures 50A-C), and allows the construction of ECD with a size smaller than one millimeter. This procedure involves coating / metallizing the unprinted substrate parts using the hydrophilicity difference of the substrate surface and the printer ink. Figures 58A-C show photographs of the initial modeled electrodes designed by the authors. Two (or more in some cases) complementary polymers will be deposited separately on patterned areas and lateral ECDs will be constructed by covering the active zone with an ion conductive medium (i.e. a gel electrolyte, an ionic liquid or a solid electrolyte) . By changing the size and shape of these electrodes, the change characteristics and modeling of the resulting ECDs can be manipulated.

The modeled electrodes allow the construction of laterally configured dual polymer electrochromic devices. As shown in Figure 38, PEDOT was deposited on 2 pixels, while PBEDOTB (OC12H25) 2 was deposited on the other two pixels. The change of these polymers in relation to a counterpolymer hidden behind these films, the ability to change from a zero contrast state to the left, where both polymers are in their highly transmitting p-doped forms, to a high contrast state in the that both polymers are neutral, demonstrates how these polymers could be used on screens or as camouflage materials. The reference invention provides numerous opportunities to control color with the numerous EC polymers of the invention and the construction of side ECDs on flexible surfaces that can range from plastic as shown, to paper or metal substrates (eg, for electrochromic documents ).

The ability to match the colors of two pairs of complementary polymers allows flexibility in the window-type ECD design. Side ECDs, in essence, ECDs operating on a single surface or using porous electrodes, can be constructed based on the color mix of two polymers deposited on a patterned surface. For example, a device, as shown in Figures 56A-B, can provide a surface that changes from deep blue absorbent to sky blue transmitter using two complementary EC materials.

A series of suitable EC polymers have been developed and can be combined to form a high contrast device or a multicolored screen after a change in polarization voltage. Figures 57A-B show photographs of some simple layers of these polymers and demonstrate how color control can be induced. The color / luminance match / contrast between two polymers will be controlled by adjusting the thickness and redox states of the polymers.

In Figure 57A, the two polymers are maintained at the same potential and are changed relative to a "hidden" counterpolymer material below through a porous electrode. Since the overall color of the device will be the sum of the two polymers, the screen state 1 will be a transmitter and will show the metal electrode below (or a printed screen), while the screen state 2 will provide a general purple color from the sum of red and blue. This is also illustrated in Figure 4; The transmitting polymers in screen state 1 provide a high contrast color surface (red and blue) in screen state 2.

True single layer devices can be constructed using pairs of polymers such as those shown in Figure 57B. In this case, the PBEDOT-Cz is a yellow transmitter in its reduced form, while the PBEDOT-V is a highly oxidized transmitter (screen 1). Changing the polarization on the device will provide the colors light blue and deep purple (screen 2). Thus, the surface can change from a light yellow to a deep blue.

Side-type devices can be constructed by addressing each EC layer independently and electrical isolation between lines or pixels is required. Typical manual screens with characteristic sizes of the order of 25-50 micrometers will make the human eye perceive "the average color". Other applications, such as signals or camouflage, allow larger feature sizes of the order of millimeters to centimeters. In non-limiting examples, the modeling of the substrate can be performed by metal vapor deposition (MVD) or linear modeling (LP). Alternatively, inkjet printing and screen printing procedures can be used for substrate modeling.

Reflective electrodes comprising any conductive metal, for example, gold, can be modeled as the conductive layer using masking and MVD. As illustrated in Figures 35A-C, three masks have been created on a brass substrate of 4.5 cm x 4.5 cm x 0.25 mm (length x width x thickness) using interdigitated electrode modeling. That has allowed the authors to deposit gold electrodes by MVD to create a laterally configured ECD.

This procedure provides satisfactory metallization of any substrate, such as glass and plastics. Among these, the porous substrates appear adequate to enhance the polymer change time as diffusion of the counterions is directed over short distances through the membranes to the counterpolymer below. Thus, ECDs can be constructed that have the schematic design shown in Figure 35E and based, for example, on porous polycarbonate membranes as metallizable substrates. Alternatively, single layer EDCs can also be constructed and, of course, any other porous or non-porous substrate can be used in the construction of these ECDs (eg, single or dual layer ECDs). These membranes can also be used in flexible ECD with high exchange rates (Chandrasekhar P., Zay BJ, Birur GC, Rawal S., Pierson EA, Kauder L., Swanson T. [2002] Adv. Fanct. Mater. 12:95 ).

Example 1- Synthesis of exemplary substituted N-alkyl pyrroles

A series of several substituted N-alkyl pyrroles according to the reference invention can be synthesized. N-alkyl substituted poly (3,4-propylenedioxypropyl) (PProDOP) were originally designed as potentially processable electrochromic polymers, with the characteristics of poly (3,4-alkylenedioxypropyl) (PXDOP) (low oxidation potential, outstanding stability against to over-oxidation and potential change and multicolored electrochromism). The N-substitution modifies the electron-rich character of the heterocycle, thus leading to a new set of colors, including purple, green, brown and blue. The electrochemical spectrum showed that the absorbance of the n-n * transition in the neutral state is shifted to blue compared to the non-N-derivatized PProDOP. In the case of poly (N-Glycol ProDOP) (N-Gly PProDOP), this transition has a maximum at 306 nm (starting at 365 nm) thus giving a highly transparent neutral polymer almost colorless with a relative luminance greater than 99% for a film thickness of approximately 200 nm. Another interesting feature of N-substituted PProDOP is its well-defined electrochemistry, where almost "ideal" behaviors are obtained with N-propyl PProDOP (N-Pr PProDOP), N-octyl PProDOP (N-Oct PProDOP) and N-glycol PProDOP (N-Gly PProDOP). For these polymers showing an E1 / 2 of less than -0.1 V versus Fc / Fc + (+ 0.2 V versus ECS), the ratio between anodic and cathodic peak currents at a scan rate of 20 mV / s is almost 1.0 and the difference between the anodic and cathodic peak potentials (LEp) is less than 8 mV. In addition, these polymers have not only shown interesting electrochromic properties in the visible. Very strong absorption is observed in the near infrared (IRC) range after doping, thus allowing the use of these polymers for the realization of devices that change in the IRC that are of great interest in military applications.

Electropolymerization was carried out with a potentiostat / electroplating model 273 from EG&G Princeton Applied Research using a platinum button working electrode (diameter: 1.6 mm; area 0.02 cm2), a platinum flag counter electrode and a reference Ag / AgNO3 (Ag / Ag +) 0.01 M. The electrolyte used was LiClO4 / PC 0.1 M. The reference was externally calibrated using a 5 mM ferrocene solution (Fc / Fc +) in the electrolyte (E1 / 2 (Fc / Fc +) = +0.070 V vs. Ag / Ag + in LiClO4 / 0.1 M PC). The potentials were calibrated against Fc / Fc + in the same electrolyte, as recommended by IUPAC46. All potentials are registered against Fc / Fc +. Electrodeposition was performed from a 0.01 M solution of monomer in the electrolyte at a scan rate of 20 mV / s. Cyclic voltammetry was carried out using the same electrode distribution using electrolyte without 0.1M LiClO4 / PC monomer. The Scribner Associates Corrware II software was used for data collection and potentiostat control.

Spectrum electrochemical spectra were recorded on a Varian Cary 5E UV-visible-IRC spectrophotometer connected to a computer at a scanning speed of 600 nm / min. A three electrode cell assembly was used where the working electrode was an ITO coated glass (7 x 50 x 0.6 mm, 20 O / �, Delta Technologies Inc.), the counter electrode was a platinum wire and a 0.01 M Ag / AgNO3 reference electrode Potentials were applied using the same EG&G potentiostat described above and the data was recorded with the Corrware II computer program for electrochemical data and with the Varian Cary Win-UV for spectral data .

General ProDOP N-alkylation procedure: 47 sodium hydride (1.2 equiv. Without mineral oil) was carefully added to the ProDOP solution (1.0 equiv.) In freshly distilled THF at room temperature. After stirring for 1 h, alkylating reagents (1.2 equiv.) Were added and the reaction mixtures were refluxed for 3-4 h. After cooling to room temperature, THF was removed by a rotary evaporator and water was added carefully. The aqueous solution was extracted with ether (3 times) and dried over MgSO4. Purification by column chromatography on silica gel using hexane / ethyl acetate provided N-alkylated ProDOP respectively. For 2d, the semi-purified product 3 was dissolved in THF and tributylammonium fluoride (1.0 M in THF) was added. Using the same procedure described above, 2d was obtained as a clear oil.

Colorimetry measurements were obtained using the Minolta CS-100 chromometer and the normal / normal (0/0) illumination / sight geometry recommended by the CIE for transmittance measurements.58 A three electrode cell similar to that of The electrochemical spectrum The potential was controlled by the same potentiostat EG&G. The sample was illuminated from behind by a D50 light source (5000 K) in a light cabin specially designed to exclude outside light. The color coordinates are expressed in the CIE Yxy 1931 color space, where the value of Y is a measure of the luminance in Cd / m2. The relative luminance, expressed in%, was calculated by dividing the value of Y measured in the sample by the value of Y0 corresponding to the background. Note that, frequently, relative luminance is recorded instead of luminance because it provides a more significant value.48

Polymer films for electrochemical spectrum were prepared by galvanostatic deposition on ITO (R s � 10 O / �). The films with ITO support were grown at 0.01 / cm2 mA in 0.1 M LiClO4 / PC containing 0.01 M monomer.

N-Me ProDOP (2a): a colorless oil; 1H NMR (300 MHz, CDCl3) 5 6.14 (s, 2H), 3.97 (m, 4H), 3.46 (s, 3H), 21.3 (m, 2H); 13C NMR (75 MHz, CDCl3) 5 129.5, 106.5, 72.8, 34.2, 24.5; FT-IR (CDCl3) 3021 (s), 1460 (m), 1371 (s), 1216 (s), 1056 (s) cm -1; EMAR (FAB) calculated for C8H11NO2 (M +) 153.0789, obtained 153.0723.

N-Pr ProDOP (2b): a colorless oil; 1 H NMR (300 MHz, CDCl 3) 5 6.17 (s, 2H), 3.97 (m, 4H), 3.59 (t, J = 7.1 Hz, 2H), 2.12 (m, 2H ), 1.71 (c, J = 7.1 Hz, 2H), 0.87 (t, J = 7.1 Hz, 3H); 13C NMR (75 MHz, CDCI3) 5 128.6, 105.7, 72.3, 51.9, 35.2, 24.3, 11.1; FT-IR (CDCl3) 3043 (s), 2989 (s), 1558 (s), 1423 (m), 1225 (s), 919 (s) cm -1; HRMS (FAB) calculated for C10H15NO2 (M +) 181,1102, obtained 181,1125.

N-Oct ProDOP (2c): a colorless oil; 1H NMR (300 MHz, CDCI3) 5 6.17 (s, 2H), 3.97 (m, 4H), 3.61 (t, J = 7.1 Hz, 2H), 2.12 (m, 2H ), 1.62 (m, 2H), 1.20 (m, 10H), 0.87 (t, J = 7.1 Hz, 3H); 13C NMR (75 MHz, CDCI3) 5 135.8, 105.7, 73.2, 72.4, 35.2, 33.1, 31.7, 29.3, 29.2, 29.1, 26 , 8, 22.6; FT-IR (CDCl3) 3055 (s), 2988 (s), 1558 (m), 1421 (m), 1265 (m), 909 (s), 706 (s) cm-1; HRMS (FAB) calculated for C15H25NO2 (M +) 251,1885, obtained 251,1901.

N-GI and ProDOP (2d): a colorless oil; 1 H NMR (300 MHz, CDCl 3) 5 6.25 (s, 2H), 3.96 (m, 4H), 3.80 (t, J = 4.9 Hz, 2H), 3.75-3.63 (m, 4H), 3.63-3.52 (m, 6H), 2.11 (m, 2H); 13C NMR (75 MHz, CDCI3) 5 138.8, 106.3, 72.5, 72.3, 71.1, 70.7, 70.4, 61.8, 50.1, 35.1; FT-IR (CDCl3) 3448 (a), 2930 (s), 2872 (s), 1557 (m), 1460 (m), 1413 (m) cm -1; EMAR (FAB) calculated for C13H21NO5 (M +) 271.1419, obtained 271.1405.

The N-substitution of 3,4-propylenedioxypyrrole (ProDOP) was carried out through an N-alkylation reaction with several alkyl chains of different length and hydrophilic character (see Figure 6). The alkyl groups used herein may vary from a short to a long chain and from a hydrophobic chain to a hydrophilic chain. The ProDOP was treated with sodium hydride and alkyl bromides were added at room temperature. The reaction mixtures were refluxed for certain times and purification by chromatography provided N-alkylated products 2a-c, respectively. For 2d, tri (ethylene glycol) mesylate protected with t-butyldimethylsilyl (TBDMS) was added to the 3,4-propylenedioxypyrrole solution after being treated with sodium hydride. After completing and purifying the reaction, deprotection by tributylammonium fluoride provided the N -tryethylene glycol ProDOP.

The oxidative electropolymerization of the monomers was carried out in propylene carbonate (PC) with 0.1 M LiClO4 as electrolyte. It should be noted that the electropolymerization characteristics of these N-substituted ProDOPs are especially sensitive to the nature of the solvent and the electrolyte used. Table 1 shows the oxidation potentials observed for the monomers during oxidation at a scan rate of 20 mV / s. As observed for pyrrole and N-alkyl pyrroles, the monomer oxidation potential of ProDOP (Eox, m = +0.58 V vs. Fc / Fc +) is greater than that of N-substituted ProDOPs. The propylenedioxy substituent at positions 3 and 4 of the pyrrole ring increases the electron-rich character of the monomer, thus leading to a lower monomer oxidation potential for ProDOP than for pyrrole. In addition, the N-alkyl substitution also increases the electronic density of the monomer by inducing effect. As a result, N-substituted ProDOPs have a lower oxidation potential than ProDOPs between +0.50 and +0.54 V versus Fc / Fc +, as shown in Table 1. Note that the oxidation potential of the monomer It increases slightly with the chain length, since oxidation of the monomer occurs at + 0.50 V for the N-Me ProDOP, + 0.51 V for the N-Pr ProDOP, + 0.52 V for the N-Oct ProDOP and +0.54 V for N-Gly ProDOP versus Fc / Fc +. This small difference could come from the impact of the alkyl chain on the nitrogen atom. A long chain probably distorts the p orbitals of nitrogen and, thus, its participation in conjugation. As a consequence, the heterocycle is less rich in electrons with a long alkyl chain in nitrogen and, therefore, oxidizes less easily.

Electropolymerization was performed for all monomers using cyclical multiple scanning voltammetry using a 0.01M monomer solution in 0.1M LiClO4 / PC. The appearance of a different peak of the redox process of the polymer at a potential less than that of Monomer oxidation (+ 0.20 V vs. Fc / Fc +) in the case of polymerization of N-Me PProDOP seems to indicate a growth that involves the coupling of soluble oligomers (Figure 7a) which, in fact, are more reactive than the monomer. 49 For the other substituted ProDOP monomers, polymerization proceeds at a slower rate. This substantial decrease in the rate of electropolymerization has been described above for N-alkylated pyrroles and was attributed to the decrease in conductivity resulting from N-substitution.50 Usually, the longer the chain, the lower the conductivity and, for therefore, slower is the electrodeposition. For example, after 20 cycles, the anodic peak current of the N-Me PProDOP is approximately 0.80 mA / cm2, while the N-Pr PProDOP barely reaches 0.054 mA / cm2 and the N-Oct PProDOP is 0.050 mA / cm2. Note that, despite a longer chain, the electrodeposition of the N-Gly PProDOP (see Figure 7d), is much faster than for the other N-alkyl PProDOP, except the N-Me PProDOP, with a peak current anodic 0.12 mA / cm2 after 20 cycles. This effect is probably the result of an increase in deposition rate induced by the more hydrophilic character of N-Gly ProDOP, which provides better adhesion to the substrate. It should be noted that all polymers studied except N-Me PProDOP have very narrow redox processes during growth. Since oxidation potentials in the middle of the curve vary linearly with the inverse of the number of repeating units, 51 this seems to indicate that the polymers formed have a narrow distribution of their chain length.

The polymers were deposited by cyclic voltammetry on a platinum electrode (area: 0.02 cm2) from a 0.01 M monomer solution in 0.1 M LiClO4 / PC electrolyte in order to compare the electrochemistry of the different N-substituted polymers and, since the polymerization rate is much slower when the chain length is increased, electrodeposition was performed only for 4 cycles for the N-Me ProDOP, 40 cycles for the N-Pr ProDOP, 5 cycles for the N-Gly ProDOP and 20 cycles for the N-Oct ProDOP. As a result, all polymers are in the same range of current densities.

Figure 8 shows the cyclic voltamogram of thin N-substituted PProDOP films at scanning rates of 50, 100, 150 and 200 mV / s in 0.1M LiClO4 / PC. It should be noted that all polymers have an oxidation potential in the middle of the relatively low curve, which is characteristic of PXDOP, and derives from the presence of the propylenedioxy substituent at positions 3 and 4. In addition, redox processes are very well observed defined and reversible with N-substituted PProDOP, which contrasts with the extensive redox processes recorded for N-alkyl pyrroles. 52 Oxidation potentials in the middle of the polymer curve (E1 / 2) are observed between -0.13 V and 0.24 V versus Fc / Fc + (see table 1). As observed for monomer oxidation potentials, the longer the N-substituent, the greater the E1 / 2. The same phenomenon has been observed for the N-alkyl pyrroles53 and is a result of the steric effect of the substituent that distorts the polymer skeleton, thus reducing the length of conjugation. It should be noted that the N-substituted PProDOP show a capacitive behavior that seems to decrease when the chain length of the N-substituent is increased. Since the capacitance is related to the amount of charge stored per unit volume, this may indicate that a longer substituent provides a less compact polymer, which results in a decrease in capacitance.

To illustrate the outstanding reversibility of redox processes, the proportions between the anodic and cathodic peak currents (ipa / ipc) and the peak separation (LEp) are reported in Table 1. Except the N-Me PProDOP, which shows a peak ratio of 1.35 and a relatively high peak separation (92 mV), all other N-substituted PProDOPs have an almost ideal ratio of 1.0 together with a very small LEp (less than 8 mV) at a scanning speed of 20 mV / s. The dependence of the scanning speed of the anodic and cathodic peak currents and the peak separation (LEp) shows a linear dependence as a function of the scanning speed as illustrated in Figure 9 for N-Pr PProDOP. This demonstrates that electrochemical processes are not limited by diffusion and are extremely reversible even at very high scan speeds. Note that the ability to change reversibly in a process not limited by diffusion at scanning rates of up to 1,000 mV s-1 is quite unusual for conductive polymers and may come from the fineness of polymer films (approximately 30 nm). Figure 9b shows the absence of significant separation of the anodic and cathodic peaks that is close to the ideal nernstian behavior in the case of the thin layer cell.54. However, the fact that the LEp increases with the scanning speed is an indication of the occurrence of load transfer problems, thus causing a speed limitation. As seen in Table 1, when the chain length of the N-substituent increases, LEp decreases, and the ratio of anodic and cathodic peak approaches 1.0, indicating that redox processes become more reversible. This effect may derive from the more porous structure, which would allow easier diffusion of dopant ions within the polymeric film. In summary, the electrochemistry of the N-substituted PProDOP has outstanding characteristics compared to polypyrrole and PProDOP, due to its very well-defined redox processes and its outstanding reversibility.

N-substituted PProDOPs have been deposited as thin films on ITO / glass substrates by galvanostatic deposition at a current density of 0.01 mA / cm2 from a 0.01 M monomer solution in 0.1M LiClO4 / PC. Note that although thin electroactive films of N-Oct ProDOP on ITO / glass can be obtained, sufficient thickness was not achieved to allow spectrochemical analysis, probably due to the strong hydrophobicity of the monomer due to the long alkyl chain. Figure 10 shows the electrochemical spectrum of N-Me PProDOP (A), N-Pr PProDOP (B) and N-Gly PProDOP (C) in 0.1 M LiClO4 / PC. As expected, N-substitution has shifted to the blue transition of nan *, which is now in the UV range with a maximum absorbance (Ammax) at 330 nm (3.75 eV) for the N-Me PProDOP and 306 nm (3.05 eV) for the N-Pr PProDOP and the N-Gly PProDOP. This corresponds to a band gap (measured at the edge of the nan * absorption band) of 3.0 eV for the N-Me PProDOP and 3.4 eV for the N-Pr PProDOP and the N-Gly PProDOP, which is higher than that of PProDOP (2.2 eV). The displacement towards the observed blue, in relation to PProDOP, can be explained by the steric effect of the N-substituent. It should be noted that the ability to introduce and control steric effects in conductive polymers is especially useful because it provides a way to control the polymer band gap and, thus, its electrochromic properties. It should also be noted that, the longer the chain, the greater the distortion of the conjugated skeleton. However, since the N-Pr and the N-Gly PProDOP have the same band gap and Amáx, a chain length of 3 carbons appears to be sufficient to achieve maximum steric effect. The significant blue shift obtained by adding an N-substituent to the ProDOP ring opens the field of colorless neutral polymers that are colored after doping (cathodic coloring polymers).

A small absorption band associated with high energy charge transporters grows after oxidation, at 2.59, 2.60 and 2.67 eV for N-Me, N-Pr and N-Gly PProDOP, respectively. Note that this small band is subsequently reduced to higher potentials in the case of N-Me PProDOP (previously -75 mV vs. Fc / Fc +) and N-Gly PProDOP (above 60 mV versus Fc / Fc +) as frequently observed in conductive electroactive polymers. After oxidation, the transition from n to n * decreases at the expense of a wide and very intense absorption band centered on the near infrared (IRC) corresponding to the low energy charge conveyors. The tail of this IRC band, as well as the intermediate band, are responsible for the color of the polymeric film, since they are located in the visible region of light. It should be noted that the neutral state of the N-Gly PProDOP only absorbs in the UV range, thus resulting in a transparent, colorless film. For N-Me and N-Pr PProDOP, a residual absorption in the neutral state that gives the polymer film its coloration (for example, purple in the case of N-Me PProDOP) is present in the visible. Even if all N-substituted PProDOPs show strong IRC absorbency in their doped state, it should be noted that the N-Gly PProDOP has a slightly different behavior at high oxidation levels. In fact, above 60 mV versus Fc / Fc +, the transition associated with low-energy charge carriers travels at longer wavelengths (lower energies). From 60 mV to 700 mV, the intensity of the last transition is increased, which corresponds to the formation of a highly oxidized but not degraded polymer. After 700 mV, a decrease in the IRC transition is observed, which probably corresponds to the start of the over-oxidation process. The transmittance (% T) of N-Gly PProDOP in the visible range of light is presented in Figure 11 for different levels of oxidation. In the neutral state (-300 mV versus Fc / Fc +), the polymer film is very transparent and transmits more than 90% of the light over the entire visible range. At an intermediate potential (+ 60 mV), the transmittance shows a minimum of 40% at approximately 470 nm. Note that, at this potential, they never transmit more than 50% of the light in the entire visible range. When the polymer reaches its maximum oxidation level (+700 mV vs. Fc / Fc +), the transmittance below 550 nm increases at the expense of transmittance at longer wavelengths. The minimum that can be seen at 470 nm has disappeared and now corresponds to a maximum of the transmittance in the visible (around 55%). These changes in the transmittance over the visible range of light have a great influence on the color of the polymer that changes from a neutral, transparent, colorless state to a blue doped state. Therefore, N-Gly PProDOP is a pure anodic coloring material, which is extremely rare among electrochromic polymers.

N-Me and N-Gly PProDOP have shown interesting electrochemical and optical properties in the previous sections. In order to further study the color changes of these polymers after doping for potential screen applications, the authors have performed an in situ colorimetric analysis of the different polymers.55 Color is the most important property for use in applications of screen and it is necessary to define it precisely. Therefore, the authors studied the polymers by colorimetry and expressed the results in the CIE 1931 Yxy and CIE 1976 L * a * b * color spaces as recommended by the "International Lighting Commission" (CIE) ) .56 The colors observed for each polymer at different levels of oxidation are summarized in Table 2. The N-Me PProDOP changes from deep purple to blue, through a dark green intermediate, after oxidation. It should be noted that an intense purple color does not have a single dominant wavelength located at the spectral site of the CIE 1931 diagram and, therefore, is the result of the sum of several absorptions located at different wavelengths in the visible range.57 In the case of the neutral N-Me PProDOP, these absorptions correspond to the limit of the transition nn * and its tail, which absorbs throughout the visible light. The color path of this polymer in the CIE 1931 Yxy color space is shown in Figure 12A. It can be clearly seen that, between -1.10 V and -0.30 V versus Fc / Fc +, the xy coordinates are almost identical, which means that there is no visible change in the color of the polymer. When the potential is increased to +0.85 V, the dominant wavelength of the light transmitted through the material decreases as a consequence of the formation of charge transporters in the polymer that absorbs at longer wavelengths. At higher potentials, the transitions associated with the charge transporters decrease in intensity, as shown by the electrochemical spectrum, thus resulting in a lower absorption at high wavelengths and, therefore, a decrease in the dominant wavelength. This behavior is quite typical for electrochromic polymers, as the authors have previously reported.55 The color path of the N-Gly PProDOP, shown in Figure 12B, has similar characteristics. However, it should be noted that the xy coordinates of this polymer in the neutral state (-0.20 V vs. Fc / Fc +) are almost identical to the white point (x = 0.349, y = 0.378), which means that the material It is colorless. As seen in Table 2, the N-Gly PProDOP changes after the Luminance, which is a coordinate of the Yxy color space, represents the brightness of a color. It also provides a lot of information since, with a single value, it provides information about the perceived transparency of a sample over the entire visible range of light. Instead of Y, it is usually more convenient to express the luminance as% Y, which corresponds to the luminance of the sample divided by the luminance of the light source. It should be noted that% Y is different from% T because it takes into account the light sensitivity of the human eye, which is not constant over the entire visible range.55,58 In fact, the human eye perceives brightness with maximum sensitivity at 550 nm (yellow light). Below 480 nm or above 650 nm, the sensitivity is ten times less than at 550 nm. The relative luminance (% Y) of N-Me and N-Gly PProDOP is presented in Figure 13. Again, the behavior of these polymers is different from that of PProDOP, which has a lower luminance when it is neutral than in the state. doped, and also presents a minimum to intermediate potentials (darker state corresponding to the brown color). The N-Me PProDOP shows a slightly lower luminance in the neutral state (27%) than in the doped state (32%). This slight change can be explained according to the electrochemical spectrum results. After oxidation, there is a transition in the visible (480 nm) associated with load transporters that increases after oxidation. In addition, the tail of the transition from n to n * is located in the visible, as well as the tail of the IRC band associated with the low energy load conveyors. After doping, the band from n to n * decreases at the expense of the transition at 480 nm and that of the IRC. This does not lead to a change in luminance. At higher potentials, the band at 480 nm is eliminated, while the IRC transition is still growing. This results in a slight decrease in the overall absorbance of the polymer in the visible and, therefore, provides the observed increase in luminance observed by colorimetry. As noted above, the behavior of N-Gly PProDOP is quite exceptional for an electrochromic polymer. This is confirmed by luminance measurements showing that the polymer film has a luminance of almost 100% in the neutral state corresponding to a colorless and completely transparent material. The luminance remains almost unchanged when the potential is increased to -0.20 V versus Fc / Fc +, then sharply decreases to approximately 55% at -0.10 V and stabilizes at this value to +0.85 V versus Fc / Fc +. The difference in behavior between the N-Gly PProDOP and the N-Me PProDOP is closely related to its band gap. In fact, the transition from n to n * in the N-Gly PProDOP is completely in the UV range and not even the tail of the transition overlaps with the visible range of light. As a consequence, the decrease in this transition has no effect on the color of the polymer. Therefore, only the transitions associated with the load conveyors give rise to a visible color. This phenomenon is even more sensitive since the neutral polymer shows no absorption in the visible. The ability to switch between a colorless neutral state and a blue-gray doped state gives this electrochromic material the little frequent property of being truly anodic in color.

In summary, a series of N-substituted PProDOPs have been prepared that show extremely reversible electrochemistry together with good electrochromic properties. The low potentials in the middle of the curve, resulting from the 3,4-propylenedioxy substitution on the pyrrole ring, give these polymers a good stability in the doped state, since air and humidity are not likely to reduce them . Therefore, the Nsubstitution allows a fine adjustment of the band gap and, therefore, of the optical properties. The ability to build a pure anodic colorant polymer has been demonstrated with N-Gly PProDOP. It should be noted that very few polymers provide this type of color change from colorless to blue after oxidation. The ease with which these new compounds can be derivatized opens a wide variety of possibilities for the production of advanced polymers for screen applications, including electrochromic devices. In particular, the introduction of appropriate substituents into the propylenedioxy ring should result in soluble polymers that may be of great interest to processable electrochromic materials in screen applications.

Example 2 - Optimization of ECD reflectors

In this example the authors address the optimization of ECDs that work in the reflector mode and are able to modulate the reflectivity in the regions of the visible, IRC and average IR of the spectrum. As a device platform that conveniently allows the characterization of the EC property in a reflective mode, the authors have used a sandwich structure of an outwardly active electrode device originally described in the patent literature [R. B. Bennett, W. E. Kokonasky, M. J. Hannan, L. G. Boxall, US Pat. UU. 5,446,577, 1995; b) P. Chandrasekhar, US Pat. UU. 5,995,273, 1999], as schematically shown in Figure 14. This ECD structure has several advantages. First, the properties of the EC material of interest can be tested through a window chosen to be highly transmitting in the wavelength range of interest. Second, all materials can be flexible, allowing significant mechanical deformation without impeding the operation of the device. Finally, using a specially designed high viscosity electrolyte, the device can be self-sealing. In this construction, gold-coated Mylar sheets are used as counter electrodes and as work electrodes. The upper electrode is cut with a series of parallel grooves, separated by approximately 2 mm, through the active surface, making it porous to ion transport during the change. The cell was mounted using a high viscosity polymer electrolyte composed of LiClO4 dissolved in a matrix of poly (methyl methacrylate) (PMMA) swollen with acetonitrile (ACN) / propylene carbonate (PC). At the edges of the device, the electrolyte ACN evaporates, leaving the PMMA and LiClO4 on PC. As the PMMA becomes insoluble, it seals the outer edges of the device and provides self-encapsulation. The use of this electrolyte further minimizes solvent evaporation, prevents leaks and allows the ECD to be tested in the long term. Both the active top layer and the counterpolymer film were electrochemically deposited on the gold-coated Mylar electrodes from 10 mM monomer solutions in LiOCl4 in 0.1M ACN at a constant potential. An electrolyte soaked separator paper was used to isolate the back of the working electrode from the counterpolymer layer. The upper layer is in contact with a window that is transmitting for the wavelengths of interest, allowing precise measurements of the reflectivity of the active layer. Normally, the authors use ZnSe for the IRC at medium IR, glass at the IRC and the visible and polyethylene for the visible through the average IR, with a somewhat lower performance of the latter because of the IR absorption bands. With this design, only the electroactive polymer that faces outward is responsible for modulating surface reflectivity, while the counter electrode polymer is used to balance the charge and coloration.

A device based on PProDOT-Me2 has been implemented as the active upper layer and poly [3,6-bis (2- (3,4-ethylenedioxy) thienyl) -N-methylcarbazole] (PBEDOT-NmeCz) as the back layer. As the upper film of the device changes from its neutral, colored state, to its p-doped, discolored state, a gradual and controllable transition from an opaque violet to a transparent pale blue is observed. This color change is due to the doping procedure that modifies the structure of the polymer's electronic band, producing new electronic states in the hole and discoloring the n-n * transition; consequently the electronic absorptions move towards smaller energies outside the visible region. As it is constructed, the device switches in 3 seconds between the two extreme electrochromic states shown. It should be noted that this change time is due to the diffusion of the ions through the gel electrolyte and along the grooves of the working electrode. Improving the design of the ECD, the use of a highly porous working electrode and increasing the electrolyte conductance, will reduce the optical response time and can enhance the color contrast of the device.

The reflectance of the sandwich structure was tested over 0.3-5 μm (0.25-4 eV) at various cell voltages. The visible and near IR data were measured in a 150 nm thick polymer film under a glass window; near infrared data in a 200 nm thick polymer film with a ZnSe window and the parasitic reflectivity of the window was subtracted. Several layers of the device of the inventors have influence on the spectra: the electrochromic polymer, the electrolyte gel and the gold electrode. In all the spectra, two strong bands of water absorption (2.8 μm) and elongation of C-H (3.3-3.4 μm) are observed; they come from both the polymer and the gel electrolyte, and are relatively constant as the polymer oxidizes and reduces. The fully reduced polymer (-1.5 V; solid line) is strongly absorbent in the visible region (0.4-0.65 μm) and, therefore, the reflectance of the device is low in this region. At wavelengths of more than 0.9 μm (1.4 eV) this polymeric layer becomes quite transparent, so that the gold layer under the polymer dominates the reflectance. At even longer wavelengths, the vibrational characteristics of the polymer are evident and the reflectance of the device decreases. When it is completely oxidized, that is, it is doped (+1.0 V), the absorption in the visible discolors and, at the same voltage, a strong infrared absorption appears, hiding the underlying gold electrode. The infrared absorption (and the contrast of the device) is stronger at approx. 1.8 μm. At this wavelength, the authors detect a reflectance contrast of more than 90%. This contrast ratio is greatly enhanced when compared to the results for PEDOT (contrast reflectance 50-55%) and polyaniline derivatives. At longer wavelengths (4-5 μm), the reflectance of the polymeric device increases somewhat with the polymer in the doped state and decreases with the polymer in the undoped state, reducing the contrast to approximately 60%. In intermediate oxidation states (0 V, -0.5, and -1 V) the device has a reflectance that is generally intermediate between that of the fully oxidized and fully reduced states. The exception to this behavior is the doping-induced band around 1-1.2 μm (1-1.2 eV), which is stronger at these intermediate levels of doping. The physical interpretation of these spectra is that the non-doped insulating polymer has its inter-band transition n-n * in the visible one and is transparent (except for vibrational absorption) in the IR region. The doping of the light produces two subhueco absorption bands, due to the presence of polar states, and a partial discoloration of the interband transition. With total doping, bipolarones are formed and the inter-polar transition is absent.

A key feature of such an ECD for displays or for thermal control applications is the life of the device, that is, the number of cycles of changes it can undergo before degradation appears. The redox stability of the cell was determined by continuously changing the device between its fully absorbent and transmitter states using a 25 s change period. After several stages of double potential, the reflectivity was measured at a fixed wavelength at which the contrast is high. The PProDOT-Me2-based cell that uses LiClO4 electrolyte makes hundreds of changes without any degradation of the working electrode. After 1500 changes, the reflectivity of the oxidized form of the polymer has the same initial value, but the neutral form exhibits a reduction of the reflectivity. As the device was mounted in the air, it is likely that the neutral oxygen-sensitive form oxidizes irreversibly during the change. The preparation of the device in an environment without oxygen or water should dramatically increase its cyclability, while opening an additional window in the region of 2.7-3.1 μm. By switching to an electrolyte based on lithium trifluoromethylsulfonylimide (3M salt) the authors have built devices that could be changed 10,000 times over a period of 6 days with a loss of contrast of approximately only 20%.

In conclusion, the authors have shown that PProDOT-Me2 provides a high EC contrast in the regions of the visible, the IRC and the average IR of the electromagnetic spectrum. The contrast ratios of 55% at 0.6 μm in visible, of more than 80% between 1.3 and 2.2 μ in the IRC and of more than 50% between 3.5 and 5.0 μm show that these Conductive polymers are excellent materials for redox reflectivity that change for a metal surface over a wide range of spectral energies.

Materials and procedures: ProDOT-Me2 was synthesized and fully characterized according to previously published procedures. The high viscosity electrolyte based on poly (methyl methacrylate) and lithium perchlorate was plasticized with polypropylene carbonate to form a transparent, highly conductive gel. To facilitate the synthesis of the gel, PMMA and LiClO4 were first dissolved in acetonitrile. The composition of the foundry solution was LiClO4 / PMMA / PC / ACN in a ratio of 3: 7: 20: 70 by weight.

The electrochemical deposition of the polymer layers was carried out using a potentiostat / electroplating model 273A from EG&G. A three electrode cell with Ag / Ag + was used as the reference electrode, Mylar gold coated as the working electrode and a platinum flag as the counter electrode to electrosynthesize polymer films.

The reflectance of the sandwich structure was measured along the infrared and visible regions using a Bruker 113v FTIR spectrometer and a Zeiss 800 MPM microscope photometer. In the average IR, the authors used a ZnSe window on the polymer and the device was included in a sealed cell to isolate it from the atmosphere. In the visible and near infrared region a glass window was used. The union of electrical conductors to the electrodes allowed the oxidation and reduction of the polymer in situ.

Example 3 - Electrochemical characterization of high band hollow polymers

This example demonstrates the electrochemical characterization of a high band hollow PProDOP derivatized with N-butanol (hereinafter, PProDOP-BuOH). The authors also report the characterization of PProDOP C-alkyl substituted polymerized in solution that are cast on electrode surfaces from common organic solvents such as chloroform and dichloromethane.

The chemical structures of the monomers used in this work are depicted in Figure 15. The chemical polymerization of C-alkyl substituted ProDOP was carried out in chloroform or methanol with ferric chloride. Independent films were prepared by filtration through a glass frit under vacuum. Electrochemical polymerization was carried out with a potentiostat / galvanostat 273A from EG&G from monomer solutions in 0.01M acetonitrile. 0.1 M Et4NOT was used as electrolyte. A platinum button electrode was used as a working electrode in a three electrode cell distribution with a platinum flag as the counter electrode and Ag / Ag + as the reference electrode. For optical measurements, polymer films were deposited galvanostatically on ITO glass at J = 0.5 mA / cm2.

PProDOP-BuOH high band hollow. The cyclic voltammetric polymerization of PProDOP-BuOH is provided in Figure 16. The propylenedioxy substituent of the pyrrole ring increases the electron-rich character of the monomer relative to pyrrole and the initiation of monomer oxidation occurs at E = 0.72V against Ag / Ag +. Irreversible monomer oxidation in the first cycle is followed by a nucleation loop as shown in the inner graph. Polymer growth occurs rapidly with little spike separation, since the redox change of the polymer is reversible. The dependence of the scanning speed of the anodic and cathodic peak currents shows a linear dependence that demonstrates that electrochemical processes are not limited by diffusion. The polymer can be reversibly changed at a scan rate of 500 mV / s. The long-term change of the polymer between the neutral and oxidized states shows a loss of current of less than 20% after 300 cycles. The UV-Vis spectrum of the neutral polymer on ITO / glass showed an n-n * transition shifted towards blue at 410 nm (~ 3 eV) due to torsion of the skeleton by the butanol substituent. After oxidation, the n-n * transition decreases at the expense of an intense absorption band in the near infrared region.

Soluble PProDOP derivatives: C-alkylated PProDOPs are chemically polymerized by ferric chloride in methanol or chloroform. Higher yields were obtained by using methanol as a solvent (~ 90%). The resulting polymers were isolated in their oxidized form and were soluble in organic solvents such as chloroform, dichloromethane and DMF. These polymers are rich enough in electrons so that the complete chemical reduction of these polymers is not possible, even in the presence of strong reducing agents (ammonia or hydrazine). Independent films with conductivities of up to 55 S / cm were prepared for PProDOP-2-ethylhexyl). The electrochemical and optical properties of the electrochemically deposited films of the C-alkylated PProDOP showed similar characteristics to those of the original PProDOP polymer.

Example 4-New functionalized derivatives of 3,4-ethylenedioxypyrrole (EDOP, 5a) and 3,4- (1,3-propylenedioxy) pyrrole (ProDOP, 5b)

This example refers to new functionalized derivatives of 3,4-ethylenedioxypyrrole (EDOP, 5a) and 3,4- (1,3-propylenedioxy) pyrrole (ProDOP, 5b) as especially electron-rich monomers that provide highly electroactive and stable conductive polymers useful for a diverse set of applications that have been synthesized. ProDOP N-alkylations were carried out to provide a variety of ProDOP derivatives with alkyl, sulfonatealkoxy, glyme and glyme alcohol side chains. Iodination of EDOP and ProDOP by iodine decarboxylation provided iodine-functionalized derivatives useful for subsequent aryl coupling chemistry. N-protection and EDOP formylation, followed by Knoevenagel condensation of the resulting 2formyl-EDOP with aryl acetonitrile derivatives, resulted in 1-cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2-thienyl) vinyl (23) (Th-CNV-EDOP) and 1-cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2- (3,4-ethylenedioxythienyl) vinyl (26) ( EDOT-CNV-EDOP.) A dioxipyrrole based on 14-crown-4-ether 34 was synthesized with a cavity potentially useful for the detection and coordination of lithium ions in the resulting electroactive polymer. 43b and 43c) containing octyl, ethylhexyl and dioctyl substituents attached to the central methylene of the propylene bridge as monomers for potentially soluble n-conjugated polymers.

The general synthetic route for 3,4-alkylenedioxypropyls is illustrated in Figure 18 and the initial set of prepared monomers is shown in Figure 17 (Thomas, CA; Zong, K .; Schottland, P .; Reynolds, JR Adv. Mater. 2000,12,222; Gaupp, CL; Zong, K .; Schottland, P .; Thompson, B. C; Thomas, CA; Reynolds, JR Macromolecules, 2000,33,1132; Schottland, P .; Zong, K. ; Gaupp, CL; Thompson, B. C; Thomas, CA; Giurgiu, I .; Hickman, R .; Abboud, KA; Reynolds, JR Macromolecules 2000, 33, 7051). These compounds (5a-5e) were synthesized from the known intermediate dimethyl-N-benzyl-3,4-dihydroxypyrrol-2,5-dicarboxylate (1), in five stages with an overall yield of 20-25%. This series of reactions (1,4-dioxane ring formation, deprotection of the benzyl group, hydrolysis and decarboxylation) provided the corresponding 3,4-ethylenedioxypyrrole (5a, EDOP) [Merz, A .; Schropp, R .; Dotted, E. Synthesis, 1995, 795], 4- (1,3-propylenedioxy) pyrrole (5b, ProDOP), 3,4- (1,4-butylenedioxy) pyrrole (5c, BuDOP), 3,4- (2- methyl-1,3-propylenedioxy) pyrrole (5d, ProDOP-Me) and 3,4- (2,2-dimethyl-1,3-propylenedioxy) pyrrole (5e, ProDOP-Me2) with moderate to good yields (Schottland, P ; Zong, K .; Gaupp, CL; Thompson, BC; Thomas, CA; Reynolds, JR; Macromolecules, 2000,33,1132).

With the original monomers available, the authors investigated the N-alkylation of ProDOP with a variety of side substituents ranging from simple alkyl groups to glyme, glyme alcohol and sulphonatealkoxy derivatives as illustrated in Figure 19. The ease of functionalization of the Pyrrol provides new derivatives with a wide range of possibilities in a simple way. Under the conditions used, ProDOP was easily rented with a moderate to good yield of 40-85%. The increased polarity of the substituents suggests that polymers derived from these monomers may ultimately prove useful as biocompatible substrates for cell growth (Thomas, CA; Zong, K .; Schottland, P .; Reynolds, JR, Adv Mater. 2000,12,222; Schmidt, CE; Shastri, VR; Vacanti, JP; Langer, R. Proc. Nat. Acad. Sci. USA, 1997,94, 8948; Houseman, BT; Mrksich, MJ Org. Chem. 1998,63, 7552) and, in the case of the sulfonate derivatized system, provide self-dopable and water soluble conductive polymers (Sundaresan, NS; Basak, S .; Pomerantz, M .; Reynolds, JRJ Chem. Soc, Chem. Commun 1987, 621; Patil, AO; Ikenoue, Y .; Wudl, F .; Heeger, AJJ Am. Chem. Soc. 1987, 109, 1858). In general, these N-derivatized ProDOPs can be isolated by column chromatography or precipitation and subsequently stored as solids / liquids under argon in the freezer before polymerization.

Next, the authors consider the introduction of halides (bromide or iodide) at positions 2 and 5 of the aromatic heterocycle in order to increase their usefulness in the preparation of multi-aryl ring monomers by means of metal-mediated coupling procedures of transition, such as the reactions of Stille, Heck and Suzuki. Using the thiophene EDOT analog as a comparison, multi-aryl ring monomers have provided a broad set of polymers with a high degree of control of their redox and optical properties (Groenendaal, LB; Jonas, F .; Freitag, D. ; Pielartzik, H .; Reynolds, JR Adv. Mater. 2000, 12, 481). EDOP bromination was attempted under various conditions, but it was not a success due to EDOP instability. Bromination by means of bromine, NBS and other reagents under standard conditions resulted in rapid and uncontrolled polymerization. The authors note that the highly electron-rich nature of EDOP, appreciable for the significantly lower oxidation potential for EDOP than for pyrrole (Thomas, CA; Zong, K .; Schottland, P .; Reynolds, JR Adv. Mater. 2000.12, 222; Gaupp, CL; Zong, K .; Schottland, P .; Thompson, B. C; Thomas, CA; Reynolds, JR Macromolecules, 2000.33,1132; Schottland, P .; Zong, K. ; Gaupp, CL; Thompson,

B. C; Thomas, C. A .; Giurgiu, I .; Hickman, R .; Abboud, K. A .; Reynolds, J. R. Macromolecules 2000, 33, 7051; Zotti, G .; Zecchin, S .; Schiavon, G .; Groenendaal, L. B. Chem. Mater. 2000,12,2996) favors this polymerization. Subsequently, a series of N-protected EDOPs, derivatized with t-BOC, tosyl, silyl and benzyl groups were synthesized and subjected to standard bromination conditions. Surprisingly, tosilo protected EDOP was very sensitive to air and moisture, providing the decomposed form. EDOP derivatives protected with t-BOC and silyl were quite stable, but not enough to withstand the subsequent oxidation reaction conditions. Finally, although the N-benzyl protected EDOP was stable enough to withstand the bromination reaction conditions without significant decomposition, bromination success could not be achieved. Alternatively, iodine decarboxylation was examined in N-benzyl-3,4-ethylenedioxypyrrol-2,5-carboxylic acid (13) using a literature procedure (Chong, R .; Clezy, PS Aust. J. Chem. 1967 , 20, 935; Merz, A .; Kronberger, J .; Dunsch, L .; Neudeck, A .; Petr, A .; Parkany, L. Angew. Chem. Int. Ed. 1999, 38, 1442), as is shown in Figure 20. The reaction was carried out without problems to provide N-benzyl-2,5-diiodo-EDOP (14) with excellent performance that was stable enough for further reactions. In an initial study using 14, transition metal-mediated coupling with 2-trimethyl-stannyl-EDOT resulted in easily oxidized 2,5-bis (2-EDOT) EDOP. As will be illustrated below, the diester / diol derivative of 3,4-dioxypyrrole can also serve as an intermediate for C-alkylation derivatives. In this case, diester 41a (scheme 3) could be selectively hydrolyzed (Gassman, P. EJ .; Schenk, WNJ Org. Chem. 1977,42, 918) by treatment with an excess of potassium t-butoxide / H2O (1 : 1) to provide the monohydrolyzed product (15). The subsequent iodine decarboxylation could be carried out in the presence of the ester to provide the monoiodinated compound 16.

In order to obtain useful EDOP monomer derivatives, it is desirable to have N-protected EDOP available with positions 2 and 5 open for additional chemical transformations. Several protecting groups were examined and the benzyl and t-BOC groups provided the most useful derivatives in terms of stability, additional reaction capacity and subsequent deprotection. As shown in Figure 21, benzyl protection of EDOP was carried out satisfactorily with a yield of 90% to provide N-benzyl-EDOP (17). In another route that begins with an EDOP precursor, the N-benzyl 2a protected 2,5-diester derivative was hydrolyzed to diacid 13 and subsequently decarboxylated by heating in triethanolamine for a short period of time to provide N-benzyl-EDOP ( 17) With excellent performance. This last route is preferred in the synthesis of 17 due to the lack of need to isolate EDOP (5a).

With a stable N-benzyl EDOP available, the authors then explored the 2-formylation of 17 by means of the Vilsmeier-Haack procedure using a literature procedure (Eachern, AM; Soucy, C; Leitch, L. C; Arnason , JT; Morand, P. Tetrahedron, 1988, 44, 2403). The Vilsmeier-Haack reagent was prepared under standard conditions (POCI3 / DMF in CH2Cl2) and, as shown in Figure 21, direct treatment of 17 with this reagent followed by hydrolysis provided aldehyde 18 in moderate yield. In another route, also shown in Figure 21, direct treatment of EDOP with the Vilsmeier-Haack reagent under similar conditions provided 2-formyl-EDOP (19) and subsequent N-protection by t-BOC provided 20 with a good performance. These formylated EDOP derivatives are very useful for additional chemical transformations such as Knoevenagel or Wittig-type reactions that can be used to incorporate EDOP into more highly conjugated monomer systems.

Recently, polymers containing alternating donor and acceptor units along the skeleton have received significant attention due to their reduced electronic band gap and the ability to undergo doping of both p-type and n-type (van Mullekom, HAM; Vekemans, JAJM; Havinga, PE; Meijer, EW Mater. Sci. Eng., 2001, 32,1). In such polymers, the authors have used the cyanovinylene unit as an electron acceptor and have reported the synthesis and electrochemical properties of polymer derivatives prepared from 1-cyano-2- (3,4-ethylenedioxythienyl) -1 - (2-thienyl) vinyl (Th-CNV-EDOT) and 1-cyano-1,2-bis (2- (3,4-ethylenedioxythienyl) vinyl (EDOT-CNV-EDOT) (Sotzing, GA; Thomas, CA; Reynolds , JR; Steel, PJ Macromolecules, 1998, 31,3750.) In this work, the authors observe that, by combining appropriate donors with the cyanovinylene acceptor polymers could be designed with a systematic adjustment of the electronic band gap from 1.1 eV at 1.6 eV (Thomas, CA; Reynolds, JR ACS Symp. Ser. 1999, 735, 367) Due to the high HOMO level of EDOP, the authors believe that this system could be especially useful for closing the band gap additionally Knoevenagel condensation of N-benzyl EDOP-aldehyde 18 with 2-thienyl acetonitrile provides 1-cyano-2 - (2- (3,4-Ethylenedioxypyrril)) - 1- (2-thienyl) vinyl N-benzyl protected 22 and subsequent deprotection using Na / NH3 provided Th-CNV-EDOP (23) in moderate performance as shown in scheme 5 (Thomas, CA; Zong, K .; Reynolds, J. R., pending publication). In this route, it was discovered that the deprotection of the benzyl group was difficult and the most commonly used procedures (solvolysis and catalytic hydrogen transfer) were not successful, requiring the use of Na / NH3. In order to overcome this problem, t-BOC-protected EDOP-aldehyde 20 was used in the reaction. As illustrated in Figure 22, condensation was carried out without problems to provide the desired product and, interestingly, occurred with concurrent deprotection. These concurrent condensation and deprotection allowed a simple reaction in a single container with excess base. It should be noted that the unprotected EDOP-aldehyde 19 did not undergo condensation under similar conditions. Extending this chemistry to an EDOT derivative, 2- (3,4-ethylenedioxythienyl) acetonitrile (25) was synthesized according to a known procedure (Sotzing, G. A .; Thomas, C. A .; Reynolds,

J. R .; Steel, PJ Macromolecules, 1998, 31, 3750) and condensation with 20 provided 1-cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2- (3,4-ethylenedioxythienyl) vinyl (EDOP-CNV -EDOT) (26) with good performance.

In addition to the potentially useful electronic and optical properties provided by polyheterocycles, ionic interactions within the material also suggest their potential in the release of ionic drugs (Pernaut,

J. M .; Reynolds, J. R. J. Phys. Chem. B. 2000,104,4080) and as ion detection materials (McQuade, D. T .; Pullen, A. P .; Swager, T. M. Chem. Rev. 2000,100.2537). In this area, the possibility of fusing complexing groups of ions directly on conjugated polymers, so that they are in direct electronic communication with the system n, is a route in which high sensitivity sensing materials can be accessible (Reddinger, JL; Reynolds , JR Chem. Mater. 1998,10, 3). In relation to the alkylene dioxypyrrole chemistry analyzed here and, for this purpose, a derivatized 14-crown-4-ether dioxypyrrole was designed and synthesized as illustrated in Figure 23, which may be potentially useful as a polymer lithium sensor. The results of polymerization, redox change and ion-dependent electrochemical change show that this polymer has a strong electrochromic response that can provide ionochromic materials (Pernaut, J.-M .; Zong, K .; Reynolds, J. R. pending publication).

To begin this synthesis, ditosylate 30 was prepared from pinacol (27) according to a literature procedure (Alston, DR; Stoddart, JF; Wolstenholme, JB; Allwood, BL; Williams, DJ Tetrahedron, 1985, 41, 2923). Diol 29 was synthesized through an O-allylation, followed by hydroboration / oxidation and subsequent tosylation to provide 30 as a dioxipyrrole 1 coupling partner. The coupling reaction was performed by the procedure developed by Murashima and his collaborators (Murashima , T .; Uchihara, Y .; Wakamori, N .; Uno, H .; Ogawa, T .; Ono, N. Tetrahedron Lett. 1996, 37, 3133) with slight modifications. To achieve good coupling performance, the traditional preparation procedure uses the simultaneous injection of the two reagents by syringe into the reflux reaction vessel. The procedure used here avoids the use of these syringes using a Dean-Stark trap and it was found to be convenient without any significant difference in performance. Deprotection of the benzyl group by catalytic hydrogen transfer and hydrolysis provided diacid 33 in good yield. Subsequent decarboxylation of 33 in hot triethanolamine provided 14-crown-4-ether 34 with a yield of 30% based on 1.

The monomers described above were designed for use in oxidative electrochemical polymerizations in which the resulting polymers are deposited on the electrode surfaces as conductive, redox active and insoluble films. This process can be especially useful when preparing polymers for electrochemical-based devices, but proves to have an especially low mass yield of polymer obtained based on the amount of monomer used. Ultimately, it is especially desirable to prepare monomer derivatives that can be polymerized using mass synthesis conditions and that will provide processable polymers in solution. Thus, a high conversion of monomer into polymer is possible. This has been demonstrated for numerous conjugated polymer systems, especially those based on polythiophenols (Handbook of Conducting Polymers, 2nd Ed., Skotheim, TA; Elsenbaumer, RL; Reynolds, JR, Eds., Marcel Dekker: New York (1998). To that end, the authors have synthesized a series of modified ProDOP monomers having alkyl chains attached to the central methylene of the propylenedioxy moiety, as illustrated in Figure 24.

Diethyl malonate was rented with octylbromide and 2-ethylhexylbromide to provide mono and dialkylated malonates 36a, 36b and 36c, respectively. After separation, the reduction of diesters with LiAlH4 resulted in diols 37a, 37b and 37c which became dimesylates 38a, 38b and 38c, respectively. The formation reaction of the alkylenedioxy ring of N-benzyl-3,4-dihydroxypyrrol-2,5-dicarboxylate (39) with the dimesylates was carried out according to the Merz8 procedure to provide the cycled products 40a, 40b and 40c with yields from moderate to good, respectively. Using the procedures used for the preparation of the XDOP series (scheme 1), the derivatized octyl and heptyl ProDOP 43a, 43b and 43c were synthesized. To date, the authors have shown that these monomers can undergo oxidative polymerization chemically and electrochemically to give rise to soluble polymers (Zong, K. Z .; Reynolds, J. R. pending publication).

The alkylenedioxypyrrole building block provides immense flexibility for the synthesis of a completely new family of electron-rich monomers for the synthesis of conductive polymers. N-alkylation allows the incorporation of lateral substituents ranging from non-polar hydrocarbon, through polar neutral species, to ionic species. ProDOPs substituted in the central methylene carbon of the alkylene bridge are readily synthesized. Having these two derivatization positions accessible while not affecting the polymerization position opens a number of additional possibilities, including those in which both the N-and C-substitution are carried out in the same molecule. The use of various protecting groups in the 3,4-alkylenedioxypyrrole nitrogen allows chemistry to be carried out successfully in the position

2. The demonstration of the successful halogenation and formylation authors in 3,4-ethylenedioxypyrrole serves as a representative synthetic intermediate for synthesis of more complex monomers. The inventors have demonstrated the utility of these derivatives through the coupling of the diiodine molecules with 2-trimethylstannil-EDOT and the formation of diheterocycle monomers linked to cyanovinylene using the formylated derivative. By controlling the chemistry of the condensed dioxy ring system, ionically interacting systems, such as the other crown ether shown here, can also be attached. All these derivatives are illustrative of the many other possibilities that alkylenedioxypropyls provide.

General ProDOP N-alkylation procedure (6, 8-11): Sodium hydride (1.2 equiv. Without mineral oil) was carefully added to a solution of ProDOP (1.0 equiv.) In freshly distilled THF at 0 ° C . After stirring for 1 h, alkylating reagents (1.2 equiv.) Were added and the reaction mixtures were refluxed for 3-4 h. After cooling to room temperature, THF was removed by a rotary evaporator and NH4Cl was added carefully. The aqueous solution was extracted with ether (3 times) and dried over MgSO4. Purification by column chromatography on silica gel using hexane / ethyl acetate provided the desired N-alkylated ProDOPs.

1- [2- (2-Ethoxy-ethoxy) -ethyl] -3,4- (1,3-propylenedioxy) pyrrole (6). After treatment, the crude product was purified by column chromatography on silica gel using hexane / ethyl acetate (2: 1) as eluent to provide the product as a colorless oil (350 mg, 40%); 1H NMR (300 MHz, CDCI3) 5 6.22 (s, 2H), 3.96 (m, 4H), 3.81 (t, J = 5.5 Hz, 2H), 3.67 (t, J = 5.5 Hz, 2H), 3.55 (m, 4H), 3.51 (c, J = 7.1 Hz, 2H), 2.11 (m, 2H), 1.20 (t, J = 7.1 Hz, 3H); FT-IR (CDCl3) 3021, 2960, 1559, 1541 cm -1; EMAR (FAB) (MH +) calculated for C13H22NO4 256.1548, obtained 256.1553.

3- [3,4- (1,3-propylenedioxy) pyrrol-1-yl] -propyl (7) sodium sulfonate. Sodium hydride (0.11 g, 4.70 mmol, washed with pentane) was carefully added to a solution of ProDOP (0.50 g, 3.60 mmol) in freshly distilled THF at 0 ° C. After stirring for 1 h, 1,3-propanesulfone (0.57 g, 4.70 mmol) was added and the reaction mixtures were refluxed for 48 H. After completion of the reaction, the resulting solid was filtered and washed with acetone repeatedly to provide the product as a white powder (1.2 g, 85%); mp> 250 ° C (decomp.); 1H NMR (300 MHz, DMSO-d6) 5 6.25 (s, 2H), 3.83 (m, 4H), 3.70 (t, J = 6.6 Hz, 2H), 2.33 (t , J = 7.1Hz, 2H1.98 (m, 2H), 1.86 (pentet, J = 7.6 Hz, 2H); 13C NMR (75 MHz, DMSO-d6) 5 137.5, 105.4, 71, 4, 48.1, 39.3, 34.8, 27.1; FT-IR (CDCl3) 3022, 1545, 1419, 1366, 1216,1185, 1060 cm-1; EMAR (FAB) (M-H +) calculated for C10H15NO5SNa 284.0568, obtained 284.0569.

N-Methyl-3,4- (1,3-propylenedioxy) pyrrole (8). After treatment, the crude product was purified by column chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide the product as a colorless oil (250 mg, 45%); 1 H NMR (300 MHz, CDCl 3) 5 6.14 (s, 2H), 3.97 (m, 4H), 3.46 (s, 3H), 2.13 (m, 2H); 13C NMR (75 MHz, CDCI3) 5 129.5, 106.5, 72.8, 34.2, 24.5; FT-IR (CDCl3) 3021,1460,1371,1216,1056 cm-1; EMAR (IE) (MH +) calculated for C8H11NO2 153.0789, obtained 153.0723.

N-propyl-3,4- (1,3-propylenedioxy) pyrrole (9). After treatment, the crude product was purified by column chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide the product as a colorless oil (150 mg, 40%); 1 H NMR (300 MHz, CDCl 3) 5 6.17 (s, 2H), 3.97 (m, 4H), 3.59 (t, J = 7.1 Hz, 2H), 2.12 (m, 2H ), 1.71 (m, 2H), 0.87 (t, J = 7.1 Hz, 3H); 13C NMR (75 MHz, CDCI3) 5 128.6, 105.7, 72.3, 51.9, 35.2, 24.3, 11.1; FT-IR (CDCI3) 3043 (s), 2989 (s), 1558 (s), 1423 (m), 1225 (s), 919 (s) cm-1; EMAR (IE) (M +) calculated for C10H15NO2 181,1102, found 181,1125.

N-octyl-3,4- (1,3-propylenedioxy) pyrrole (10). After treatment, the crude product was purified by column chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide the product as a colorless oil (220 mg, 48%); 1 H NMR (300 MHz, CDCl 3) 5 6.17 (s, 2H), 3.97 (m, 4H), 3.61 (t, J = 7.1 Hz, 2H), 2.12 (m, 2H ), 1.62 (m, 2H), 0.87 (t, J = 7.1 Hz, 3H); 13C NMR (75 MHz, CDCI3) 5 135.8, 105.7, 73.2, 72.4, 35.2, 33.1, 31.7, 29.3, 29.2, 29.1, 22 , 6; FT-IR (CDCI3) 3055, 2988, 1558, 1421, 1265, 909, 706 cm-1; EMAR (IE) (M +) calculated for C15H25NO2 251.1885, found 251.1901.

2- (2- {2- [3,4- (1,3-Propylenedioxy) pyrrol-1-yl] -ethoxy} -ethoxy) -ethanol (12). The semi-purified product 11 was dissolved in THF and tetrabutylammonium fluoride (1.0 M in THF) was added and stirred for 1 h at room temperature. After treatment, the crude product was purified by column chromatography on silica gel using hexane / ethyl acetate (1: 1) as eluent to provide the product as a colorless oil (0.5 mg, 55%); 1H NMR (300 MHz, CDCI3) 5 6.25 (s, 2H), 3.96 (m, 4H), 3.80 (t, J = 4.9 Hz, 2H), 3.75-3.63 (m , 4H), 3.63-3.52 (m, 6H), 2.11 (m, 2H); 13C NMR (75 MHz, CDCI3) 5 138.8, 106.3, 72.5, 72.3, 71.1, 70.7, 70.4, 61.8, 50.1, 35.1; FT-IR (CDCI3) 3448, 2930, 2872, 1557, 1460, 1413 cm -1; EMAR (IE) (M +) calculated for C13H21NO5 271.1419, obtained 271.1405; Anal. Calcd. For C13H21NO5: C, 57.55; H, 7.80; N, 5.16. Obtained: C, 57.28; H, 7.64; N, 5.05.

N-benzyl-3,4-ethylenedioxypyrrol-2,5-dicarboxylic acid (13). The diester 2a (10 g, 0.03 mmol) was suspended in an aqueous solution of 3M NaOH (150) and ethanol (10-20 ml) was added as a co-solvent. The reaction mixture was stirred vigorously at 70-80 ° C for 6 h. After cooling to 0 ° C in an ice water bath, the reaction mixture was carefully acidified with concentrated HCl. The resulting white precipitate was collected by filtration and washed with water twice to give the diacid as a white powder (8.6 g, 95%); mp 219 ° C (decomp); 1 H NMR (300 MHz, DMSO-d6) 5.12.80 (a, 2H), 7.25 (m, 3H), 6.85 (m, 2H), 5.74 (s, 2H), 4.22 (s, 4H); 13 C NMR (75 MHz, DMSO-d6) 5 161.8, 140.6, 137.1, 129.1, 127.5, 126.7, 111.7, 65.8, 47.8; EMAR (FAB) (MH +) calculated for C15H14NO6 304.0821, obtained 304.0820.

N-benzyl-2,5-diiodo-3,4-ethylenedioxypyrrole (14) (iodo-decarboxylation). Diacid 13 (0.5 g, 1.65 mmol) was dissolved in an aqueous solution of sodium carbonate (7.7 g, 72.6 mol) in 30 ml of water. A solution of iodine (0.92 g, 3.69 mmol) and potassium iodide (2.0 g, 12.11 mmol) in water was prepared. The diacid solution was titrated slowly by dissolving iodine and potassium iodide at room temperature. As the red color of the iodine quickly disappeared in the reaction process, a white precipitate formed. After stirring for 30 minutes after completion of the addition, a white precipitate was collected by filtration and washed with water several times to remove inorganic compounds to provide N-benzyl-2,5-diiodo-3,4-ethylenedioxypyrrole (14) as a white powder (0.56 g, 85%): mp 154-155 ° C; 1 H NMR (300 MHz, CDCl 3) 5 7.25 (m, 3H), 6.99 (m, 2H), 5.09 (s, 2H), 4.26 (s, 4H); 13C NMR (75 MHz, CDCI3) 5 137.7, 137.3, 128.5, 127.3, 126.4, 110.1, 66.5, 53.7; ERAM (FAB) (M +) calculated for C13H11NO2I2 466.8879, obtained 466.8805; Anal. Calc. For C3H11NO2I2: C, 33.43; H, 2.37, N, 3.00. Obtained: C, 34.17; H, 2.42; N, 2.94.

2-Ethoxycarbonyl-3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole-5-carboxylic acid (15). To a solution of diester 41a (4.0 g, 10.11 mmol) in THF was added potassium t-butoxide (4.5 g, 40.44 mmol) and H2O (0.73 g, 40.44 mmol ) at 0 ° C. After stirring for 30 minutes, the reaction mixture was stirred at room temperature overnight. THF was removed on a rotary evaporator and the residue was diluted with water, cooled in ice water and acidified with concentrated hydrochloric acid to provide a pale yellow precipitate. After filtering, the product was washed with water and dried in vacuo to provide a pale yellow solid as a monohydrolyzed compound. A pale yellow solid (3.3 g, 90%): mp 156-157 ° C; 1H NMR (300 MHz, CDCI3) 5 9.06 (s, 1H), 7.60 (a, 1H), 4.37 (c, J = 7.1 Hz, 2H), 4.28 (dd, J = 11.5, 2.7 Hz, 1H), 4.24 (dd, J = 11.5, 3.3 Hz, 1H), 4.05 (dd, J = 14.8, 6.6 Hz, 1H), 4.00 (dd, J = 14.8, 6.6 Hz, 1H), 2.30 (m, 1H), 1.36 (t, J = 7.1 Hz, 3H), 1, 40-1.20 (m, 11H), 0.87 (m, 6H); 13C NMR (75 MHz, CDCl3) 5 161.2, 159.6, 129.6, 112.3, 110.0, 101.4, 76.7, 76.2, 61.0, 40.2, 36 , 1, 32.9, 31.6, 28.7, 25.9, 23.1, 14.3, 14.0, 10.5; EMAR (FAB) (MH +) calculated for C19H30NO6 368,2073, obtained 368,2070; Anal. Calcd. For C19H29NO6: C, 62.11; H, 7.96; N, 3.81. Obtained: C, 62.32; H, 7.57; N, 3.73.

Ethyl 2-iodo-3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole-5-carboxylate (16). The procedure used here is similar to that of compound 15. A light yellow oil (0.3 g, 60%); 1 H NMR (300 MHz, CDCl 3) 5 8.63 (s, 1 H), 4.34 (q, J = 6.5 Hz, 2 H), 4.15 (dd, J = 11.5, 2.7 Hz , 1H), 4.10 (dd, J = 11.5, 3.3 Hz, 1H), 3.94 (dd, J = 12.1, 7.1 Hz, 1H), 3.82 (dd, J = 12.1, 7.1 Hz, 1H), 2.24 (m, 1H), 1.34 (t, J = 7.1 Hz, 3H), 1.39 - 1.15 (m, 11H ), 0.91-0.82 (m, 6H); 13C NMR (75 MHz, CDCl3) 5 160.1, 139.5, 128.7,110.1, 76.3, 76.2, 60.3, 40.5, 36.2, 32.9, 31.7 , 28.7, 25.9, 23.1, 14.5, 14.0, 10.5; FT-IR (CDCl3) 3440, 2963, 2931, 2892, 1690, 1525 cm -1; EMAR (FAB) (MH +) calculated for C18H29NO4I 450.1141, obtained 450.1104.

N-benzyl-3,4-ethylenedioxypyrrole (17). A solution of EDOP (1.0 g, 8.0 mmol) in THF was cooled to 0 ° C and sodium hydride without mineral oil (0.27 g, 12 mmol) was added. After stirring for 20 min, benzyl bromide (1.3 g, 8.0 mmol) in THF was added and the reaction mixture was stirred for 6 h at room temperature. The reaction mixture was concentrated under reduced pressure, diluted with ether, washed thoroughly with water and dried over MgSO4. After concentrating, the residue was purified by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide a white crystalline product (1.5 g, 90%): mp 6970 ° C; 1 H NMR (300 MHz, CDCl 3) 5 7.31 (m, 3H), 7.10 (m, 2H), 6.10 (s, 2H), 4.83 (s, 2H), 4.18 (s , 4H); 13C NMR (75 MHz, CDCI3) 5 138.1, 128.5, 127.7, 127.1, 110.0, 101.7, 65.8, 53.9; FT-IR (CDCl3) 3021, 2980, 2920, 1553, 1425, 1374,1365 cm -1; HRMS (FAB) (MH +) calculated for C13H14NO2 216,1024, obtained 216,1025; Anal. Calc. For C13H13NO2: C, 72.54; H, 6.09; N, 6.51. Obtained: C, 72.30; H, 6.04; N, 6.46.

N-benzyl-3,4-ethylenedioxypyrrole (17) from decarboxylation. A round bottom flask was filled with triethanolamine and heated at 180 ° C under argon with vigorous stirring. The diacid 13 (8.5 g, 28.0 mmol) was quickly added as a part and stirred vigorously for 10 minutes. The reaction mixture was cooled to room temperature and poured into water. After extraction with methylene chloride (100 ml x 3), the combined organic phases were washed with water, dried over MgSO4 and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (deactivated with triethylamine) using hexane / ethyl acetate (3: 1) as eluent to provide a white crystalline product (5.4 g, 90%): mp 69-70 ° C ( identical to 17).

N-Benzyl-2-formyl-3,4-ethylenedioxypyrrole (18). The Vilsmeier reagent was prepared by a procedure according to the literature (Eachern, A. M .; Soucy, C; Leitch, L. G; Arnason, J. T .; Morand, P. Tetrahedron, 1988, 44, 2403). POCI3 (0.71 g, 4.65 mmol) was added to a solution of DMF (0.34 g, 4.65 mmol) in methylene chloride (3.0 ml) at 0 ° C and the mixture was allowed to reaction will reach room temperature. Then, the solution was slowly added to a solution of N-benzyl-3,4-ethylenedioxypyrrole (1.0 g, 4.65 mmol) in methylene chloride (5.0 ml) at 0 ° C and allowed to reach room temperature. After stirring for 12 h, an excess of 3.0 M NaOH solution was added and stirred for 2 hours in a hot water bath. The reaction mixture was extracted with methylene chloride (25 ml x 3) and the combined organic phases were dried over MgSO4. Purification of the residue was carried out by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to obtain the product as a white solid (0.8 g, 70%): mp 75 ° C; 1 H NMR (300 MHz, CDCl 3) 5 9.53 (s, 1 H), 7.26 (m, 3 H), 7.20 (m, 2 H), 6.44 (s, 1 H), 5.36 (s , 2H), 4.29 (m, 2H), 4.20 (m, 2H); 13C NMR (75 MHz, CDCI3) 5 175.0, 149.9, 137.6,131.5,128.6, 127.6, 127.4, 114.5, 114.1, 66.0, 65.2, 52.1; FT-IR (CDCl3) 3021, 2825, 2720, 1646 cm -1; EMAR (FAB) (MH +) calculated for C14H14NO3 244.0973, obtained 244.0983; Anal. Calc. For C14H13NO3: C, 69.12; H, 5.39; N, 5.76. Obtained: C, 69.00; H, 5.41; N, 5.74.

2-Formyl-3,4-ethylenedioxypyrrole (19). POCI3 (1.67 g, 10.92 mmol) was added to a solution of DMF (0.84 g, 11.44 mmol) in methylene chloride (5.0 ml) at 0 ° C and the mixture was allowed to reaction will reach room temperature. Then, the reaction mixture was slowly added to a solution of 3,4-ethylenedioxypyrrole (1.3 g, 10.40 mmol) in methylene chloride (5.0 ml) at 0 ° C and allowed to reach room temperature . After stirring for 12 h, an excess of 3.0 M NaOH solution was added and stirred for 2 hours in a hot water bath. The reaction mixture was extracted with methylene chloride (40 ml x 3) and the combined organic phases were dried over MgSO4. Purification of the residue was carried out by chromatography on silica gel using hexane / ethyl acetate (2: 1) as eluent to obtain the product as a white solid (1.5 g, 65%): mp 147 ° C; 1H NMR (300 MHz, CDCI3) 5 9.43 (s, 1H), 9.02 (a, 1H), 6.62 (d, J = 3.8 Hz, 1H), 4.24 (m, 4H) ; Anal. Calc. For C7H7NO3: C, 54.90; H, 4.61; N, 9.15. Obtained: C, 55.03; H, 4.48; N, 9.14.

N-BOC-2-Formyl-3,4-ethylenedioxypyrrole (20). To a solution of aldehyde 19 (0.8 g, 5.2 mmol) in dichloromethane was added (BOC) 2O (1.1 g, 5.2 mmol), triethylamine (1.1 g, 10.4 mmol) and 4-dimethylaminopyridine (DMAP) (61 mg, 0.5 mmol). The reaction mixture was stirred for 3 h and concentrated under reduced pressure. The residue was purified by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide a colorless crystalline product (1.2 g, 90%): mp 94-95 ° C; 1 H NMR (300 MHz, CDCl 3) 5 10.24 (s, 1 H), 6.88 (s, 1 H), 4.38 (m, 2 H), 4.22 (m, 2 H), 1.60 (s , 9H); 13 C NMR (75 MHz, CDCl 3) 5 180.9,148,8,143,2,134,2,116,6,107.9, 85.1, 66.1, 64.9, 27.9; FT-IR (CDCl3) 2930, 2859, 1653, 1544, 1460, 1380, 1322 cm -1; Anal. Calcd. For C12H15NO5: C, 56.91; H, 5.97; N, 5.53. Obtained: C, 56.90; H, 5.80; N, 5.73.

N-Benzyl-1-cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2-thienyl) vinyl (22): To a solution of aldehyde 18 (0.60 g, 2.47 mmol ) and 2-thiophenoacetonitrile (0.34 g, 2.72 mmol) in t-butanol was added potassium t-butoxide (0.61 g, 5.43 mmol) at room temperature. The reaction mixture was stirred for 3 h at 50 ° C. After cooling to room temperature, the t-butanol was removed on a rotary evaporator and the residue was diluted with dichloromethane, washed with water and dried over MgSO4. The residue was purified by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to give the product as a yellow solid that was subjected to a debenzylation in the next step. 1 H NMR (300 MHz, CDCI3) 5 7.18 (m, 3H), 7.19 (m, 2H), 7.13 (m, 2H), 6.99 (m, 1H), 6.96 (s , 1H), 6.44 (s, 1H), 4.97 (s, 2H), 4.35 (m, 2H), 4.27 (m, 2H).

1-Cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2-thienyl) vinyl (Th-CNV-EDOP) (23): A solution of compound 22 (0.9 g, 2, 6 mmol) in THF was added very slowly to a solution of sodium (0.15 g. 6.5 mmol) in NH3 (30 mL) at -78 ° C. The reaction mixture was stirred for 3 h and a 1.0 M aqueous solution of NH4CI (20 ml) was added carefully. The lid of the vessel was removed and the reaction was allowed to reach room temperature. After evaporation of NH3, the aqueous phase was extracted with dichloromethane and dried over MgSO4. The residue was purified by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent to provide a yellow crystalline product (0.45 g, 50%): mp 164-165 ° C; 1H NMR (300 MHz, CDCI3) 5 8.60 (a, 1H), 7.30 (s, 1H), 7.16 (m, 2H), 7.02 (dd, J = 4.9, 7, 3 Hz, 1H), 6.55 (d, J = 3.3 Hz, 1H), 4.30 (m, 2H), 4.22 (m, 2H); FT-IR (CDCl3) 3460, 2989, 2930, 2202, 1575, 1538, 1343 cm -1; EMAR (FAB) (M +) calculated for C13H10N2O2S 258.0463, obtained 258.0457; Anal. Calc. For C13H10N2O2S: C, 60.45; H, 3.90; N, 10.85. Obtained: C, 60.35; H, 3.89; N, 10.91.

1-Cyano-2- (2- (3,4-ethylenedioxypyrril)) - 1- (2- (3,4-ethylenedioxythienyl) vinyl (EDOT-CNV-EDOP) (26) The procedure used was the same as the of compound 22. However, it should be noted that the BOC group was removed in the condensation process, which is advantageous with respect to the previous procedure A yellow crystalline product (1.20 g, 75%) was obtained; mp 148 ºC (decomp); 1H NMR (300 MHz, CDCI3) 5 8.60 (a, 1H), 7.34 (s, 1H), 6.49 (d, J = 3.8 Hz, 1H), 6, 25 (s, 1H), 4.40-4.15 (m, 8H); FT-IR (CDCl3) 3459, 2989, 2934, 2.859, 2202, 1569, 1531, 1459, 1344 cm-1; EMAR (FAB) ( MH +) calculated for C15H13N2O4S 317.0596, obtained 317.0601; Anal. Calc. For C15H12N2O4S: C, 56.95; H, 3.82, N, 8.86. Obtained: C, 56.44; H, 3 , 89; N, 8.61.

The known compounds 28-30 were synthesized by the method according to the literature (Alston, D. R .; Stoddart, J. F .; Wolstenholme, J. B .; Allwood, B. L .; Williams, D. J. Tetrahedron, 1985,41, 2923).

2,3-Dialyloxy-2,3-dimethylbutane (28). A transparent oil (12.5 g, 85%); 1 H NMR (300 MHz, CDCl 3) 5 5.89 (m, 2H), 5.27 (m, 2H), 5.07 (m, 2H), 3.89 (m, 4H), 1.18 (s , 12H).

2,3-Di- (3-hydroxypropoxy) -2,3-dimethylbutane (29). A transparent oil (8.2 g, 75%); 1 H NMR (300 MHz, CDCl 3) 5 3.75 (m, 4H), 3.57 (m, 4H), 1.76 (m, 4H), 1.15 (s, 12H).

2,3-Di- (3- [p-toluenesulfonyloxy] propoxy) -2,3-dimethylbutane (30). Colorless crystals (8.9 g, 80%); mp 123-124 ° C (liras. (Alston, D. R .; Stoddart, J. F .; Wolstenholme, J. B .; Allwood, B. L .; Williams, D. J. Tetrahedron, 1985, 41, 2923) 123124 ° C); 1 H NMR (300 MHz, CDCI3) 5 7.78 (d, J = 8.2 Hz, 4H), 7.31 (d, J = 8.2 Hz, 4H), 4.09 (t, J = 6 , 0 Hz, 4H), 3.35 (t, J = 6.0 Hz, 4H), 2.43 (s, 6H), 1.79 (pent, J = 6.0 Hz, 4H), 0, 96 (s, 12H).

Dimethyl 14-benzyl-6,6,7,7-tetramethyl-3,4,6,7,10,11-hexahydro-2H, 9H, 14H- [1,4,8,11] tetraoxaciclotetradecino [2,3c] pyrrolo-13,15-dicarboxylate (31). Compound 31 was synthesized by a literature procedure with some modifications (Murashima, T .; Uchihara, Y .; Wakamori, N .; Uno, H .; Ogawa, T .; Ono, N. Tetrahedron Lett. 1996, 37 , 3133). A large Dean-Stark trap was fitted in a round bottom flask with two mouths (1 l). The Dean-Stark trap was filled with a solution of diol 1 (5.0 g, 15.0 mmol) and ditosylate 30 (6.5 g, 12.0 mmol) in DMF (45 ml). Acetonitrile (450 ml) was added to the two-mouth round bottom flask followed by the addition of CsF (9.1 g, 60.0 mmol). The reaction mixture was refluxed for 24 hours under argon and cooled to room temperature. The solvent was removed on a rotary evaporator and poured into water. The aqueous phase was washed with ether (150 ml x 3) and the combined organic phases were washed with water and dried over MgSO4. The residue was purified by chromatography on silica gel using hexane / ethyl acetate (2: 1) as eluent to provide a colorless solid (2.71 g, 45%): mp 92-93 ° C; 1H NMR (300 MHz, CDCl3) 5 7.22 (m, 3H), 6.90 (m, 2H), 5.99 (s, 2H), 4.13 (t, J = 5.0 Hz, 1H ), 3.80 (s, 6H), 3.77 (t, J = 5.5 Hz, 1H), 1.93 (pent, J = 5.5 Hz, 1H), 1.21 (s, 12H ); FT-IR (CDCl3) 3022, 2963, 1718, 1700, 1653, 1559, 1541, 1442 cm -1; HRMS (FAB) (M +) calculated for C27H37NO8 503.2519, obtained 503.2524; Anal. Calcd. For C27H37NO8: C, 64.40; H, 7.41; N, 2.78. Obtained: C, 64.22; H, 7.36; N, 2.67.

Dimethyl 6,6,7,7-tetramethyl-3,4,6,7,10,11-hexahydro-2H, 9H, 14H- [1,4,8,11] tetraoxa-cyclootetradecino [2,3-c] pyrrolo-13.15 dicarboxylate (32). To a solution of 31 (3.0 g, 5.64 mmol) in acetic acid (100 ml), 10% Pd (C) (0.6 g) was added carefully in one part. The reaction flask was purged with a stream of hydrogen using a balloon containing hydrogen and another hydrogen balloon was fitted over the reaction flask. The reaction mixture was vigorously stirred for 48 h at 80-85 ° C (it should be noted that new hydrogen balloons were added depending on the reaction scale). After cooling to room temperature, the reaction mixture was filtered through a celite pad and concentrated under reduced pressure. Purification of the residue by silica gel chromatography using hexane / ethyl acetate (3: 1) as eluent afforded 32 as a pale yellow solid (32 g, 2.21%): mp 106-107 ° C; 1 H NMR (300 MHz, CDCl 3) 5 8.80 (a, 1 H), 4.19 (t, J = 5.5 Hz, 1 H), 3.88 Acid 6,6,7,7-tetramethyl-3, 4,6,7,10,11-hexahydro-2H, 9H, 14H- [1,4,8,11] tetraoxacyclotetra-decino [2,3-c] pyrrolo-13,15-carboxylic acid (33). The diester 32 (2.5 g, 6.1 mmol) was suspended in 3M NaOH (50 ml) and ethanol was added as a cosolvent (10 ml). The reaction mixture was stirred for 6 hours at 60 ° C and cooled to room temperature. The reaction mixture was extracted with ether to remove all unreacted starting material and by-products and the basic aqueous phase was cooled to 0 ° C. Acidification by conc. HCl. provided white solids after filtration (2.27 g, 97%). The resulting diacid was used in the next step without further purification.

6,6,7,7-Tetramethyl-3,4,6,7,10,11-hexahydro-2H, 9H, 14H- [1,4,8,11] tetraoxacyclotetra-decino [2,3-c] pyrrole (3. 4). The decarboxylation process is similar to that of compound 17. A light brown solid (1.50 g, 73%); mp 48-50 ° C; 1H NMR (300 MHz, CDCl3) 7.09 (a, 1H), 6.27 (d, J = 3.3 Hz, 2H), 4.04 (t, J = 5.5 Hz, 1H), 3.76 (t, J = 6.0 Hz, 1H), 1.90 (pentet, J = 5.5 Hz, 1H), 1.18 (s, 12H); 13C NMR (75 MHz, CDCI3) 5 113.0, 102.9, 80.6, 69.9, 59.2, 31.0, 21.5; FT-IR (CDCl3) 3487, 3021, 1653, 1579, 1542, 1227 cm -1; EMAR (FAB) (MH +) calculated for C16H28NO4 298,2018, obtained 298,2012; Anal. Calc. For C16H27NO4: C, 64.62; H, 9.15, N, 4.71. Obtained: C, 64.47; H, 8.98; N, 4.50.

Diethyl 2- (2-ethylhexyl) malonate (36b). To a solution of NaOEt in ethanol was added diethyl malonate (20.0 g, 0.13 mol) and 2-ethylhexyl bromide (25.1 g, 0.13 mol) at room temperature. The reaction mixture was stirred for 6 hours and the ethanol was removed on a rotary evaporator. A dilute solution of HCl was added and extracted with ether (100 ml x 3). The combined ether phases were dried over MgSO4, concentrated and purified by distillation under reduced pressure (125-126 ° C, 3.0 mmHg, lit. (Nikishin, G. I .; Ogibin, Y. N .; Petrov, A.

DJJ Gen. Chem. USSR (Trad. English), 1960, 3510) 126-127 ° C, 3.0 mmHg) to provide 36b as a clear oil (17.7 g, 50%): 1 H NMR (300 MHz, CDCl3) 4 , 20 (c, J = 7.1 Hz, 1H), 3.41 (t, J = 7.7 Hz, 1H), 1.84 (m, 2H), 1.40-1.15 (m, 15H), 0.95-0.80 (m, 6H).

Diethyl 2-octyl malonate (36a). A transparent oil (15.4 g, 45%); eg 128-130 ° C (3.0 mmHg) (lit. (Shono, T .; Matsumura, Y .; Tsubata, K .; Sugihara, YJ Org. Chem. 1982, 47, 3090), 110-123 ° C, 0.9 -1.0 mmHg); 1H NMR (300 MHz, CDCl3) 4.20 (c, J = 7.1 Hz, 4H), 3.30 (t, J = 7.1 Hz, 1H), 1.87 (m, 2H), 1 , 30-1.10 (m, 15H), 0.87 (t, J = 7.1 Hz, 6H).

Diethyl 2,2-dioctyl malonate (36c). A transparent oil (17.2 g, 38%); eg 155-156 ° C (3.0 mmHg) (lit. (Leznoff,

C. D .; Drew, D. M. Can. J. Chem. 1996, 74, 307; Uckert, F .; Setayesh, S .; Mullen, K. Macromolecules, 1999, 32, 4519), 200 ° C, 0.1 kPa); 1H NMR (300 MHz, CDCI3) 4.20 (q, J = 7.1 Hz, 4H), 1.85 (m, 4H), 1.38-1.07 (m, 30H), 0.86 ( t, J = 6.6 Hz, 6H).

2- (2-ethylhexyl) -1,3-propanediol (37b). To a solution of diester 36b (10.0 g, 36.7 mmol) in dry ether was added LiAIH4 (2.8 g, 73.4 mmol) at 0 ° C. The reaction mixture was stirred for 6 h at room temperature and water (approx. 10 ml) was added carefully. The reaction mixture was stirred for 1 h and allowed to stand to precipitate the salts. A clear ether phase was carefully decanted and the combined phases were dried over MgSO4. Purification of the crude product by silica gel chromatography using hexane / ethyl acetate (2: 1) as eluent gave diol 37b as a clear oil (4.8 g, 70%): 1 H NMR (300 MHz, CDCI3) 3 , 80 (dd, J = 10.4, 7.3 Hz, 2H), 3.61 (dd, J = 10.4, 8.2 Hz, 2H), 2.65 (s, 2H), 1, 84 (m, 1H), 1.38-1.20 (m, 9H), 1.20-1.08 (m, 2H), 0.90 (t, J = 6.6 Hz, 3H), 0 , 83 (t, J = 7.7 Hz, 3H).

2-Octyl-1,3-propanediol (37a). A colorless crystal (5.2 g, 75%) (lit.31); mp 45-46 ° C; 1H NMR (300 MHz, CDCl3) 3.83 (dd, J = 10.4, 3.3 Hz, 2H), 3.66 (dd, J = 11.0, 7.7 Hz, 2H), 2, 42 (s, 2H), 1.78 (m, 1H), 1.40-1.20 (m, 14H), 0.88 (t, J = 6.6 Hz, 3H).

2,2-Dioctyl-1,3-propanediol (37c). A transparent oil (6.5 g, 65%) (lit. (Leznoff, CD; Drew, DM Can. J. Chem. 1996, 74, 307; Uckert, F .; Setayesh, S .; Mullen, K. Macromolecules , 1999, 32.4519); 1H NMR (300 MHz, CDCl3) 3.56 (d, J = 4.4, 4H), 2.50 (s, 2H), 1.40 - 1.15 (m, 28H), 0.88 (t, J = 6.6 Hz, 6H).

General procedure for the preparation of ditosylates 38a, 38b, and 38c: To a solution of diol (1.0 equiv.) And toluenesulfonyl chloride (2.0 equiv.) In dichloromethane, a solution of triethylamine was added dropwise (2.5 equiv.) And 4-dimethylaminopyridine (0.1 mol%) in dichloromethane at room temperature. The reaction mixture was stirred for 3 h and concentrated under reduced pressure. The residue was dissolved in ether, washed with water several times and dried over MgSO4. The solvent was removed and the residue was used in the next step without further purification after drying under vacuum.

Diethyl N-benzyl-3,4-dihydroxypyrrol-2,5-dicarboxylate (39): The preparation of 39 is similar to that of 1. Colorless crystals (hot methanol, 80%); mp 146 ° C; 1H NMR (300 MHz, CDCI3) 7.81 (s, 2H), 7.23 (m, 3H), 6.91 (m, 2H), 5.78 (s, 2H), 4.32 (c, J = 7.1 Hz, 1H), 1.25 (t, J = 7.1 Hz, 6H); 13 C NMR (75 MHz, CDCl 3) 5 162.8, 139.8, 139.3, 128.6, 127.1, 125.7, 111.2, 61.4, 49.5, 14.4; Anal. Calc. For C17H19NO6: C, 61.25; H, 5.75; N, 4.20. Obtained: C, 61.00; H, 5.75; N, 4.21.

General procedure for the preparation of diethyl (N-benzyl-3,4-2-alkyl-1,3-propylenedioxy) pyrrol-2,5-dicarboxylate (40a, 40b and 40c): To a mixture of N-benzyl- Potassium 3,4-dihydroxypyrrol-2,5-dicarboxylate (39) (7.5 g, 22.6 mmol) and ditosylate 38a (7.8 g, 22.6 mmol) in dry DMF was added potassium carbonate (15.6 g, 0.1 mol) at room temperature. The reaction mixture was stirred for 12 h at 110 ° C under argon. After cooling to room temperature, the reaction mixture was poured into ice water and extracted with ether. The combined ether phases were dried over MgSO4 and concentrated on a rotary evaporator. Purification by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent gave the product as a light yellow oil.

Diethyl N-benzyl-3,4- (2-octyl-1,3-propylenedioxy) pyrrole-2,5-dicarboxylate (40a). A pale yellow oil (8.2 g, 75%); 1H NMR (300 MHz, CDCl3) 7.20 (m, 3H), 6.90 (m, 2H), 0.94 (s, 2H), 4.26 (c, J = 7.1 Hz, 1H) , 4.21 (dd, J = 8.2, 3.3 Hz, 2H), 3.98 (dd, J = 12.1, 6.6 Hz, 2H), 2.22 (m, 1H), 1.50-1.20 (m, 14H), 1.26 (t, J = 7.1 Hz, 6H), 0.88 (t, J = 6.6 Hz, 3H).

Diethyl N-benzyl-3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole-2,5-dicarboxylate (40b). A pale yellow oil (7.80 g, 71%); 1H NMR (300 MHz, CDCl3) 7.21 (m, 3H), 6.91 (m, 2H), 0.94 (s, 2H), 4.26 (c, J = 7.1 Hz, 1H) , 4.22 (dd, J = 11.5, 2.7 Hz, 2H), 3.88 (dd, J = 11.5, 7.1 Hz, 2H), 2.35 (m, 1H), 1.40-1.23 (m, 11H), 1.26 (t, J = 7.1 Hz, 6H), 0.90 (t, J = 6.0 Hz, 3H), 0.86 (t , J = 7.1 Hz, 3H); 13C NMR (75 MHz, CDCl3) 5 160.5, 142.6, 139.2, 128.2, 126.7, 126.1, 114.0, 75.9, 75.8, 60.4, 48 , 8, 40.0, 36.3, 32.9, 32.3, 28.7, 26.0, 23.0, 1.41, 13.9, 10.5.

Diethyl N-benzyl-3,4- (2,2-dioctyl-1,3-propylenedioxy) pyrrol-2,5-dicarboxylate (40c). A pale yellow oil (5.60 g, 25%); 1H NMR (300 MHz, CDCI3) 7.20 (m, 3H), 6.85 (m, 2H), 5.89 (s, 2H), 4.24 (c, J = 7.1 Hz, 1H) , 3.90 (s, 4H), 1.50-1.10 (m, 34H), 0.87 (t, J = 6.6 Hz, 6H); 13C NMR (75 MHz, CDCI3) 5 160.9, 143.3, 137.7, 128.6, 127.1, 126.5, 114.2, 79.4, 61.0, 49.5, 44 , 4, 32.5, 32.4, 31.0, 30.0, 29.9, 23.5, 23.3, 14.6, 14.5; FT-IR (CDCl3) 3023, 2965, 1716, 1437, 1365, 1291 cm -1; HRMS (FAB) (MH +) calculated for C36H56NO6 598.4107, obtained 598.4114; Anal. Calc. For C36H55NO6: C, 72.33; H, 9.27; N, 2.34. Obtained: C, 72.19; H, 9.41; N, 2.14.

Debenzylation of 40a, 40b and 40c: A reaction mixture of 40a (5.0 g, 10.3 mmol), anisole (1.5 g, 13.4 mmol), H2SO4 (0.7 g, 7.0 mmol ) in trifluoroacetic acid was refluxed for 0.5 hours at 90 ° C. After cooling to room temperature, trifluoroacetic acid was removed on a rotary evaporator and the residue was neutralized with saturated aqueous sodium bicarbonate. The aqueous phase was extracted with ether (3 x 100 ml) and the combined ether phases were dried over MgSO4. Purification by chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent provided the product.

Diethyl 3,4- (2-octyl-1,3-propylenedioxy) pyrrol-2,5-dicarboxylate (41a): A pale yellow oil (2.80 g, 72%); 1H NMR (300 MHz, CDCI3) 8.70 (a, 1H), 4.32 (c, J = 7.1, 4H), 4.15 (dd, J = 11.5, 3.3 Hz, 2H ), 4.05 (dd, J = 12.1, 6.6 Hz, 2H), 2.18 (m, 1H), 1.45-1.20 (m, 14 H), 1.35 (t , J = 7.1 Hz, 6H), 0.87 (t, J = 7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3) 5 159.8, 141.7, 110.7, 75.6, 60.7, 42.4, 31.8, 29.6, 29.4, 29.2, 28 , 0, 27.0, 22.5, 14.3, 13.9; FT-IR (CDCl3) 3446, 3022, 2980, 1700, 1653, 1526, 1459 cm -1.

Diethyl 3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole-2,5-dicarboxylate (41b). A pale yellow oil (2.53 g, 70%); 1H NMR (300 MHz, CDCI3) 8.65 (a, 1H), 4.37 (c, J = 7.1, 4H), 4.24 ( dd, J = 12.1, 3.3 Hz, 2H), 3.97 (dd, J = 12.1, 7.1 Hz, 2H), 2.30 (m, 1H), 1.36 (t , J = 7.1 Hz, 6H), 1.40-1.22 (m, 11 H), 0.91-0.83 (m, 6H); 13C NMR (75 MHz, CDCl3) 5 159.1, 140.9, 110.0, 75.3, 75.2, 59.9, 39.4, 35.4, 32.1, 31.4, 27 , 9, 25.2, 22.2, 13.6, 13.2, 9.7.

Diethyl 3,4- (2,2-dioctyl-1,3-propylenedioxy) pyrrol-2,5-dicarboxylate (41c). A pale yellow oil (3.50 g, 65%); 1H NMR (300 MHz, CDCI3) 8.61 (s, 1H), 4.33 (c, J = 7.1, 4H), 3.94 (s, 4H), 1.35 (t, J = 7 , 1 Hz, 6H), 1.45 - 1.18 (m, 28H), 0.87 (t, J = 6.6 Hz, 6H); 13C NMR (75 MHz, CDCI3) 5 159.7, 142.0, 110.5, 79.2, 60.7, 43.8, 31.8, 30.4, 29.4, 29.2, 22 , 7, 22.6, 22.5, 14.3, 13.9; FT-IR (CDCl3) 3444, 2932, 2858, 1701, 1530, 1483, 1276 cm -1; EMAR (FAB) calculated for C29H49NO6 (MH +) 508.3638, obtained 508.3641.

Hydrolysis of 41a, 41b and 41c: The procedure used is the same as that used for the preparation of compound

13.

3,4- (2-Octyl-1,3-propylenedioxy) pyrrole-2,5-dicarboxylic acid (42a): A white powder (2.50 g, 92%); mp 165-167 ° C; 1H NMR (300 MHz, DMSO-d6) 10.70 (a, 1H), 4.02 (dd, J = 11.5, 2.7, 2H), 3.91 (dd, J = 12.1, 6.0 Hz, 2H), 2.05 (m, 1H), 1.40-1.20 (m, 14H), 0.84 (t, J = 7.1, 3H); HRMS (FAB) (MH +) calculated for C17H25NO6 340.1760, obtained 340.1735; Anal. Calc. For C17H25NO6: C, 60.16; H, 7.42; N, 4.13. Obtained: C, 60.54; H, 7.67; N, 4.10.

3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole-2,5-dicarboxylic acid (42b). A white powder (2.20 g, 85%); mp 164165 ° C, 1H NMR (300 MHz, DMSO-d6) 10.70 (a, 1H), 4.02 (dd, J = 12.0, 2.7, 2H), 3.85 (dd, J = 12.0, 6.0 Hz, 2H), 2.10 (m, 1H), 1.40-1.17 (m, 11H), 0.89 (t, J = 7.1 Hz, 3H), 0, 86 (t, J = 6.6, 3H); 13C NMR (75 MHz, DMSO-d6) 5 160.3, 140.6, 111.0, 74.8, 74.8, 39.5, 34.9, 32.1, 30.6, 27.8 , 25.1, 22.2, 13.6, 10.1; HRMS (FAB) (MH +) calculated for C17H26NO6 340.1760, obtained 340.1735; Anal. Calc. For C17H25NO6: C, 60.16; H, 7.42; N, 4.13. Obtained: C, 60.07; H, 7.56; N, 3.98.

3,4- (2,2-dioctyl-1,3-propylenedioxy) pyrrole-2,5-dicarboxylic acid (42c): A white powder (2.5 g, 85%); mp 125-127 ° C; 1 H NMR (300 MHz, DMSO-d6) 10.70 (s, 1 H), 3.78 (s, 4 H), 1.50 - 1.02 (m, 28 H), 0.84 (t, J = 7 , 1, 6H); FT-IR (CDCl3) Decarboxylation of diacids 42a, 42b and 42c: The procedure used here is the same as that for the preparation of N-benzyl-3,4-ethylenedioxypyrrole (17).

3,4- (2-octyl-1,3-propylenedioxy) pyrrole (43a). An off-white solid (1.20 g, 85%); mp 79-80 ° C; 1H NMR (300 MHz, CDCI3) 5 7.25 (a, 1H), 6.28 (d, J = 3.3 Hz, 2H), 4.01 (dd, J = 11.5, 2.2, 2H ), 3.85 (dd, J = 11.6, 6.6 Hz, 2H), 2.05 (m, 1H), 1.50-1.20 (m, 14H), 0.88 (t, J = 6.6 Hz, 3H); 13C NMR (75 MHz, CDCl3) 5 139.4, 103.1, 76.7, 43.6, 31.8, 29.8, 29.4, 29.2, 27.4, 27.1, 22 , 5, 13.9; FT-IR (CDCl3) 3489, 3021, 2963, 2931, 1653, 1545, 1495, 1380 cm -1; HRMS (FAB) (MH +) calculated for C15H26NO2 252.1963, obtained 252.1963; Anal. Calc. For C15H25NO2: C, 71.67; H, 10.02; N, 5.57. Obtained: C, 71.76; H, 9.94; N, 5.19.

3,4- [2- (2-ethylhexyl) -1,3-propylenedioxy] pyrrole (43b). A pale yellow oil (0.50 g, 40%); 1H NMR (300 MHz, CDCl3) 5 7.10 (a, 1H), 6.30 (d, J = 3.3 Hz, 2H), 4.01 (dd, J = 12.1,2.7,2H), 3 , 76 (dd, J = 11.5, 6.6 Hz, 2H), 2.15 (m, 1H), 1.40 1.20 (m, 11H), 0.89 (t, J = 6, 0 Hz, 3H), 0.86 (t, J = 7.7 Hz, 3H); 13C NMR (75 MHz, CDCI3) 5 113.9, 103.1, 76.5, 76.4, 41.3, 36.2, 33.0, 31.2, 28.7, 26.1, 23 , 9, 23.1, 14.0, 10.5; FT-IR (CDCl3) 3490, 2962, 2931, 1543, 1459,1322 cm-1; EMAR (FAB) (MH +) calculated for C15H26NO2 252.1963, obtained 252.1965; Anal. Calc. For C15H25NO2: C, 71.67; H, 10.02; N, 5.57. Obtained: C, 71.44; H, 9.98; N, 5.21.

3,4- (2,2-dioctyl-1,3-propylenedioxy) pyrrole (43c). A pale brown oil. Full characterization was not achieved due to its high instability. 1H NMR (300 MHz, CDCI3) 5 7.10 (a, 1H), 6.30 (d, J = 3.3 Hz, 2H), 3.89 (s, 4H), 1.50 1.00 ( m, 28H), 0.85 (t, J = 7.1Hz, 6H).

Support information available: 1 H NMR spectra of 6, 7, 8, 9,10, 13, 14,16, 22, 26, 32, 37a, 37b, 37c, 40a, 40b, 40c, 41a, 41b and 41c. This material is available online at pubs.acs.org.

Example 5 - Electrochromic devices as platforms for studying characteristics in the visible and infrared in conductive polymers

The substituted poly (3,4-propylenedioxythiophene) dimethyl (PProDOT-Me2) can be used as a cathodic dye layer for ECD. [Welsh, D. M .; Kumar, Anil; Meijer, E. W .; Reynolds, J. R. Adv. Mater. 1999, 11, 1379]. The PProDOT-Me2 shows an extremely high contrast, with an L% T = 78% at Amáx (578 nm), a wavelength at which the human eye is highly sensitive. In addition, it shows a 60% luminance change, measured by colorimetric analysis. [Thompson, B. C; Schottland, P .; Zong, K .; Reynolds, J. R. Chem. Mater. 2000, 12, 1563]. In addition, the PProDOT-Me2 changes quite quickly, producing the optical changes mentioned above in 0.2-0.4 seconds. These enhanced electrochromic properties, in relation to the original unsubstituted PEDOT and PProDOT, are probably due to a more open morphology of the films, allowing rapid ion exchange during doping. In addition, its high coloring efficiency (200 cm2 / C) translates into the need for lower charge densities to perform a change cycle, thus providing longer lifespan for the devices.

Ideally, an anodic colorant polymer having a high band gap (Eg)> 3.0 eV (<410nm) with the n-n * transition within the ultraviolet region of the spectrum is chosen. In addition to the necessary complementary optical properties, proper ECD operation requires a high degree of electrochemical reversibility and compatibility. Recently, the group of authors has explored the possibility of obtaining "truly anodic" coloring polymers based on the newly discovered 3,4-alkylenedioxypropyl family [Zong, K .; Reynolds, J. R. J. Org. Chem. 2001, 66, 6873]. The original polymer of this family, poly (3,4-ethylenedioxypyrrole) (PEDOP), provides the lowest oxidation potential of any polymer registered to date due to the highly electron-rich nature of the dioxipyrrole monomer repeated unit. Since the pyroles have somewhat high LUMO levels, the band gaps for the PEDOP (2.0 eV) and the propylene bridge analog (PProDOP, 2.2 eV) are higher than their corresponding thiophene (PEDOT and PProDOT) . In order to increase the band gap further, the authors have prepared a series of N-substituted ProDOPs [Sonmez, G .; Schottland, P .; Zong, K .; Reynolds, J. R. pending presentation]. The N-alkyl substitution increases the electron density of the monomer and also induces a torsion in the polymer skeleton, therefore, the N-substituted ProDOPs show a band gap higher than the non-derivatized ProDOP. Of this series of polymers, ProDOP-NPrS stands out as the best candidate for use in an ECD, due to its relatively fast deposition rate, its good film quality and a more saturated color in the doped state.

Different ECD designs can be used as tools to explore the optical properties of newly discovered polymers with different levels of doping and over a wide range of the electromagnetic spectrum. This can be achieved using the ECD that faces outward in reflector mode. Another objective is to study the interaction and complementarity of two electrochromic polymers for transmission / absorption window applications, where it is crucial to match the oxidation potential and the number of active sites of the polymer. High quality dual polymer electrochromic devices can be achieved for use in broadband and high contrast devices.

The electrochemical deposition of the polymer layers was carried out using a potentiostat / electroplating model 273A from EG&G. A three-electrode cell with Ag / Ag + was used as the reference electrode, gold-coated Mylar or ITO / glass as the working electrode and a platinum flag as the counter electrode to electrosynthesize polymer films. The electrochemical spectrum was carried out using a Varian Cary 5 spectrophotometer. The colorimetry results were obtained by using a Minolta CS-100 chromometer.

The reflectance of the outward-facing device was measured along the infrared and visible regions using a Bruker 113v FTIR spectrometer and a Zeiss 800 MPM microscope photometer. In the average IR, the authors used a ZnSe window on the polymer and the device was included in a sealed cell to isolate it from the atmosphere. In the visible and near infrared region a microscope slide glass was used. The union of electrical conductors to the electrodes allowed the oxidation and reduction of the polymer in situ.

Transmission / absorption ECD. In this study, the authors compare two ECDs (with a scheme as shown in Figure 25A-B) that have the same cathodic coloration layer (PProDOT-Me2), but different anodic coloration polymers, such as PBEDOT-NMeCz and PProDOT -NPrS. Both devices have the ability to operate at low applied voltages (± 1.0 V), both films being compatible in the same electrochemical environment. This considerably increases its half-life up to 86% color retention after

20,000 cycles The devices change from a discolored state to a colored, dark state in less than 1 second, which makes them useful as fast electrochromic screens. Most importantly, while the PBEDOT-NMeCz is yellow in the neutral form and blue in the doped form, the newly discovered PProDOP-NPrS has the ability to switch between a colorless neutral state and a gray-green doped state, which possesses the Uncommon property of being a truly anodic coloring material. In addition, the doped PProDOP-NPrS widens the dark state absorption peak of the ECD in both the 400-500 nm region and the 700-800 nm region of the visible spectrum, where the contribution of the nn * transition of the film of PProDOT-Me2 is small. The complementary polymer-based devices of PProDOP-NPrS and PProDOT-Me2 show an optical contrast of approximately 70% to Amáx as well as a global luminance change of 53%, changing from a transparent state to a very dark state, almost opaque.

The authors, in their efforts to widen the absorption peak while retaining the high contrast of the transmission ECDs, have explored the possibility of having two polymers of cathodic coloration with different Amax. The authors have used PEDOP (Amáx at 520 nm) and PProDOT-Me2 (Amáx at 580 nm). At + 1V, both polymers are in their oxidized form and the electrode is shown transparent. As the potential began to reduce to -1V, the peak corresponding to the n-n * transition of the PProDOT-Me2 layer could be seen at 580 nm. In order to observe the transition of the n-n * band of the PEDOP film, an additional potential reduction to -2V was necessary. When both polymers reached the neutral state, a widening could be seen, as well as a large increase in the absorption peak.

ECD reflectors. As a device platform that conveniently allows the characterization of the EC property in a reflective mode, the authors have used an external electrode active sandwich structure originally described in the patent literature, [Bennett, R. B .; Kokonasky, W. E .; Hannan,

M. J .; Boxall, L. G. in US Pat. UU. 5,446,577, 1995; b) Chandrasekhar, P. in US Pat. UU. 5,995,273, 1999; each of these patents is incorporated herein by reference in its entirety] as shown schematically in Figure 25. In this case, PProDOT-Me2 is the top layer and PBEDOT-NMeCz is the back layer. As the upper film of the device changes from its neutral, colored state, to its p-doped, discolored state, a gradual and controllable transition from an opaque violet to a transparent pale blue is observed. The authors have shown that the PProDOT-Me2-based device provides high EC contrast in the visible, IRC and IRM regions of the electromagnetic spectrum [Schwendeman, L; Hwang, J .; Welsh, D. M .; Tanner, D. B .; Reynolds, J. R. Adv. Mater. 2001, 13, 634]. The contrast ratios of 55% at 0.6 μm in visible, of more than 80% between 1.3 and 2.2 μ in the IRC and of more than 50% between 3.5 and 5.0 μm show that these Conductive polymers are excellent materials for redox reflectivity that change for a metal surface over a wide range of spectral energies. The devices have an outstanding utility, undergoing 10,000 changes with a loss of contrast of only approximately 20%.

Example 6 - ECD transmitters

One of the objectives of this example is to enhance the lifespan under changing conditions and the contrast of ECD transmitters, and also adjust the function of the device across the entire visible spectrum. The concept for producing such a device is the use of polymer layers having different Amax. By overlapping the conductive polymer layers, not only is more of the visible spectrum covered, but the absorbance of the device is also enhanced. This performance was achieved by the construction of a laminated transmitter device based on PEDOP / PProDOT-ME2 as the anodic coloration layers and the N-propyl sulphonate derivative of high-pitched PProDOP (PProDOP-NPrS) as the anode coloring polymer . The device changes in approximately 0.5 seconds from a light blue transmitter state to a deep dark blue absorption state, with a change in transmittance of 55% at 577 nm (I. Giurgiu, DM Welsh, K. Zong, JR Reynolds, pending publication).

Example 7 -N-substitution of 3,4-propylenedioxypyrrole (ProDOP)

Electropolymerization was carried out with a potentiostat / electroplating model 273 from EG&G Princeton Applied Research using a platinum button working electrode (diameter: 1.6 mm; area 0.02 cm2), a platinum flag counter electrode and a reference Ag / AgNO3 (Ag / Ag +) 0.01 M. The electrolyte used was LiClO4 / PC 0.1 M. The reference was externally calibrated using a 5 mM ferrocene solution (Fc / Fc +) in the same electrolyte (E1 / 2 (Fc / Fc +) = +0.070 V vs. Ag / Ag + in LiClO4 / 0.1 M PC). The potentials were calibrated against Fc / Fc + in the same electrolyte, as recommended by IUPAC59. All potentials are registered against Fc / Fc +. Electrodeposition was performed from a 0.01 M solution of monomer in the electrolyte at a scan rate of 20 mV / s. Cyclic voltammetry was carried out using the same electrode distribution and using the 0.1M LiOCl4 / PC electrolyte. The Scribner Associates Corrware II software was used for data collection and potentiostat control.

Spectrum-electrochemical measurements were carried out using a Varian Cary 5E UV-visible-IRC spectrophotometer connected to a computer at a scanning speed of 600 nm / min. A three electrode cell assembly was used where the working electrode was an ITO coated glass (7 x 50 x 0.6 mm, 20 O / 0�, Delta Technologies Inc.), the counter electrode was a platinum wire and a 0.01 M Ag / AgNO3 reference electrode. The potentials were applied to the same EG&G potentiostat described above and the data was recorded with the Corrware II computer program for electrochemical data and with the Varian Cary Win-UV for spectral data. .

Colorimetry measurements were obtained using a Minolta CS-100 chromometer and the normal / normal geometry (0/0) of illumination / sight recommended by the CIE for transmittance measurements.58 As regards the electrochemical spectrum, a cell was used. Three electrodes The potential was controlled by the same potentiostat EG&G. The sample was illuminated from behind by a D50 light source (5000 K) in a light booth designed to exclude outside light. The color coordinates are expressed in the Yxy 1931 color space of the CIE, where the value of Y is a measure of the luminance in Cd / m2. The relative luminance, expressed in%, was calculated by dividing the value of Y measured in the sample by the value of Y0 corresponding to the background. Note that, frequently, relative luminance is recorded instead of luminance because it provides a more significant value.

Polymer films for electrochemical spectrum were prepared by galvanostatic deposition on ITO (Rs 10 O / �). The films with ITO support were grown at 0.01 / cm2 mA in 0.1 M LiClO4 / PC containing 0.01 M monomer.

Synthesis of monomer. In this example, the N-substitution of 3,4-propylenedioxypyrrole (ProDOP) was carried out through an N-alkylation with several alkyl chains with different lengths and hydrophilic / hydrophobic character (see Figure 26). The ProDOP was treated with sodium hydride and alkyl bromides were added at room temperature. The reaction mixtures were refluxed for certain times and purification by chromatography provided N-alkylated products 2a-c respectively. For 2d, tri (ethylene glycol) t-butyldimethylsilyl (TBDMS) protected mesylate was added to the ProDOP solution after being treated with sodium hydride. After the reaction was completed and purified, deprotection by tetrabutylammonium fluoride provided N-Gly ProDOP. To obtain the sulfonated monomer 2e, the ProDOP was treated with NaH in dry THF and 1-propanesulfonate was subsequently added at room temperature. The reaction mixture was refluxed for 24 hours and purification by chromatography provided sodium ProDOP-N-propyl sulfonate in 85% yield.

Electrochemical polymerization. The 2a-d monomers were electropolymerized / deposited from solutions containing 10 mM monomer in 0.1 M LiClO4 / propylene carbonate (PC). The 2e electropolymerization was carried out in a mixture of PC and water (94: 6). The presence of a small amount of water allows the solubility of the monomer that is otherwise insoluble in acetonitrile (ACN), N, N-dimethylformamide (DMF) or PC. Table 1 shows the monomer peak oxidation potentials (Ep, m) monitored during cumulative growth at a scan rate of 20 mV / s. Comparable with the relationship between pyrrole and N-alkyl pyrroles, the oxidation potential of ProDOP (Eóx, m = + 0.58 V versus Fc / Fc +) is greater than that of N-substituted ProDOPs. The propylenedioxy substituent at positions 3- and 4- of the pyrrole ring increases the electron-rich character of the monomer, thus leading to lower monomer oxidation potentials. In addition, the N-alkyl substitution increases the electronic density in the redox center through inductive effects and the resulting monomers have oxidation potentials even lower than the original ProDOP. The oxidation potential of the monomer is minimally increased with the chain length (+ 0.50 V for N-Me ProDOP, + 0.51 V for N-Pr ProDOP, + 0.52 V for N-Oct ProDOP and + 0.54 V for N-Gly ProDOP vs. Fc / Fc +). The oxidation potential for monomer 2e is lower than that of the other N-substituted ProDOPs (+0.25 V vs. Fc / Fc +). This could be due to the fact that N-PrS ProDOP forms more stable radical cations, the positive charge being balanced by the negatively charged sulfonate end group.

The potentiodynamic polymerizations of the 2a-e monomers are shown in Figure 27. In all cases, it is observed that the redox process of the low potential polymer evolves quite well. In the case of the polymerization of N-Me PProDOP (Figure 27A), the appearance of a different peak of the redox process of the polymer at a potential lower than the monomer oxidation (+ 0.20 V vs. Fc / Fc +) may indicate a growth that involves the coupling of soluble oligomers, which are more reactive than the monomer itself. For monomers 2b and 2c, polymerization proceeds at a much slower rate. This substantial decrease in the electropolymerization rate for N-alkylated pyrroles has been reported previously and was attributed to a decrease in conductivity resulting from N-substitution. Generally, the longer the substituent, the lower the conductivity of the resulting film and, therefore, the slower its electrodeposition. For example, after 20 cycles, the anodic peak current of the N-Me PProDOP is approximately 0.80 mA / cm2, while the N-Pr PProDOP barely reaches 0.054 mA / cm2 and the N-Oct PProDOP is 0.050 mA / cm2. Note that, despite having a longer chain, the electrodepositions of the N-Gly PProDOP and the N-PrS ProDOP (Figures 27D and 27E, respectively) are much faster than those of the other N-alkyl PProDOP, except the N -Me PProDOP. This increase in deposition rate is probably induced by the more hydrophilic character of the substituents, which provides better adhesion to the substrate. It should be noted that all polymers studied, with the exception of N-Me PProDOP, have very narrow redox processes during cumulative growth. Since oxidation potentials in the middle of the curve vary linearly with the inverse of the number of repeating units, this seems to indicate that the resulting polymers have a narrow molecular weight distribution.

Polymer characterization The polymers were deposited by cyclic voltammetry on a platinum button electrode (area: 0.02 cm2) from a 0.01 M monomer solution in 0.1 M LiClO4 / PC electrolyte in order to compare the electrochemical behavior of different N-substituted polymers, and since the polymerization rate is much slower when the chain length is increased, electrodeposition was performed for 4 cycles for N-Me ProDOP, 5 cycles for N-Gly ProDOP , 20 cycles for N-Oct ProDOP, 40 cycles for N-Pr ProDOP and for galvanostatically for N-PrS ProDOP at a current density of 0.04 mA / cm2 with a total load of 10 mC / cm2. As a result, all polymers are in a relatively narrow range of current densities.

Figure 28 shows cyclic voltamograms of thin films of N-substituted PProDOP at scanning rates of 50, 100, 150 and 200 mV / s in LiClO4 / PC 0.1 M. Well-defined and reversible redox processes are observed with PProDOP N- substituted in contrast to the extensive redox processes recorded for N-alkyl pyrroles. The oxidation potentials in the middle of the polymer curve (E1 / 2) are between -0.10 V and -0.25 V versus Fc / Fc + (see table 1). As observed for the oxidation potentials of the monomer, the longer the Nsubstituent, the higher the E1 / 2 (N-PrS ProDOP being the exception), a phenomenon also observed for Nalkyl pyrroles. This could be a result of the substituent distorting the polymer skeleton and decreasing the degree of conjugation. The capacitive behavior of these materials decreases with an increase in the length of the N-substituent. The authors attribute this to a drop in electronic conductivity as intercatenary interactions are reduced as the length of the side chain increases.

Figure 29 shows the VC of the N-PrS PProDOP prepared in the absence of supporting electrolyte. Although the authors have observed well-defined and reversible redox processes in films prepared in the presence of (Figure 28E) and without electrolyte, the fact that the current densities are comparable at the same scanning speeds, leads to the conclusion that the polymer is autodopante.

To illustrate the outstanding reversibility of these redox processes, the proportions of anodic and cathodic peak current (ipa / ipc) and peak separation (LEp) are reported in Table 1. With the exclusion of N-Me PProDOP, which shows a peak ratio of 1.35 and a relatively high peak separation (92 mV), all other N-substituted PProDOPs have an almost ideal ratio of 1.0 together with a very small LEp (less than 8 mV) at a scanning speed of 20 mV / s. The dependence of the scanning speed of the anodic and cathodic peak currents and the peak separation (LEp) shows a linear dependence as a function of the scanning speed as illustrated in Figure 30A for the N-PrS PProDOP. This demonstrates that electrochemical processes are not limited by diffusion and are reversible, even at very high scan speeds. The ability to change reversibly in a process not limited by diffusion at scanning rates of up to 500 mV s-1 is quite unusual for conductive polymers and may come from the fineness of polymer films (approximately 30 nm). As seen in Table 1, the LEp decreases with increasing length of the substituents and the proportion of the anodic and cathodic peaks approaches 1.0, indicating that redox processes become more reversible. In summary, the electrochemistry of the N-substituted PProDOP shows well-defined redox processes and outstanding reversibility compared to polypyrrole and PProDOP.

The stability of the polymer for long-term changes between oxidized and neutral states is an important feature for the use of these materials in device applications. We have monitored changes in the currents and potentials of anodic and cathodic peak of a 0.12 μm film of N-PrS PProDOP, prepared by galvanostatic deposition at a constant current density of 0.04 mA / cm2. The film was subjected to cycles

10,000 times with a scanning speed of 100 mV / s in LiOCl4 / PC 0.1 M. Figure 30B shows the slow increase in both anodic and cathodic peak currents during the first thousands of cycles. This is followed by a slow decrease, so that after 10,000 cycles the response to the polymer current is close to its initial value. The overall load involved in the electrochemical process was calculated for each voltamogram and the total charge lost during this experiment decreases by less than 8% after 5,000 cycles and less than 30% after 10,000 cycles. This demonstrates that N-PrS PProDOP films can change many times between oxidized and reduced states with relatively small changes in electroactivity, making this polymer a good candidate for electrochromic applications.

Spectrum electrochemistry Thin films of N-substituted PProDOP were deposited on ITO / glass substrates using a galvanostatic deposition at a current density of 0.01 mA / cm2. Electroactive films of N-Oct ProDOP on ITO / glass could be obtained, but were not thick enough to allow spectrochemical analysis, probably due to the strong hydrophobicity of monomer conferred by the long alkyl chain. Figure 31 shows the electrochemical spectrum of N-Me PProDOP (A), N-Pr PProDOP (B), N-Gly PProDOP (C) and N-PrS PProDOP (D) in LiClO4 / PC 0.1 M. As expected , the N-substitution has shifted the transition of nan *, which is now in the UV range, to blue, with an Amáx at 330 nm (3.75 eV) for the N-Me PProDOP, 340 nm (3.65 eV) for the N-PrS PProDOP and 306 nm (4 eV) for the N-Pr PProDOP and the N-Gly PProDOP. This corresponds to a band gap (measured at the nan * absorption band edge) of 3.0 eV for the N-Me PProDOP, 2.9 eV for the N-PrS PProDOP and 3.2 eV for the others polymers, which are considerably higher than that of PProDOP (2.2 eV). The blue shift relative to PProDOP can be explained by the steric effect of the N-substituent. The ability to control the band gap with steric interaction is especially useful for electrochromic polymers, since it can easily obtain a wide variety of colors in a single family of polymers. The significant blue shift obtained by adding an N-substituent to the ProDOP ring opens the use of these materials as anodic colored polymers, which are colorless in the neutral state and are colored after doping, although they undergo their redox changes to a potential low enough to provide the long service lives shown above. The N-Gly PProDOP and the N-PrS PProDOP neutral absorb only in the UV range, which causes them to be transparent and colorless, while the N-Me and the N-Pr PProDOP maintain a residual coloration (for example light purple in the case of the N-Me PProDOP).

After oxidation, the transition from n to n * decreases at the expense of a wide and very intense absorption band centered on the near infrared (IRC) corresponding to the low energy charge conveyors. The tail of this IRC band, as well as an intermediate band in the visible region, are responsible for the coloring of the polymer films. The intensity of this coloration is, at the most, moderate in comparison with the colored neutral states of the original PProDOP or dioxythiophene polymers.

The visible light transmittance (% T) of the N-Gly PProDOP at different levels of doping is presented in the figure

32. In the neutral state (-300 mV versus Fc / Fc +), the polymer film is highly transparent and transmits more than 90% of the light throughout the visible spectrum. At an intermediate potential (+60 mV), the transmittance shows a minimum of 40% at approximately 470 nm. When the polymer reaches its maximum oxidation level (+700 mV), the transmittance below 550 nm increases at the expense of the transmittance at longer wavelengths. The minimum transmittance seen at 470 nm disappears and now corresponds to a maximum transmittance in the visible (around 55%). These changes in the transmittance over the visible range of light have a great influence on the color of the polymer, which changes from a neutral, transparent, colorless state to a blue doped state. Therefore, N-Gly PProDOP is a pure anodic coloring material, which is extremely rare among electrochromic polymers. On the other hand, with similar optical properties, the N-PrS PProDOP has several advantages over the N-Gly PProDOP. For example, the deposition rate is much faster, the quality of the film is better, the conductivities of the films are higher and the colors obtained are more saturated.

Conductivity and processability of the N-PrS PProDOP. Independent N-PrS PProDOP films were prepared by galvanostatic deposition on glassy carbon electrodes from PC and water solutions

(94: 6) containing 0.01 M monomer with and without 0.1 M LiClO 4 at room temperature. The ambient temperature conductivities of these independent films were measured using the four-point probe technique and found to be below, in the range of 10-4-10-3 S / cm, according to the results of which It is reported in the literature for N-substituted pyrrole derivatives. The resulting polymer films were completely soluble in water in both neutral and oxidized forms. Due to the electropolymerization process used, the monomer consumption is quite low due to its design, making polymer yields low. Even in the best cases, the electropolymerization yields are of the order of 5-10%.

Independent films of N-PrS PProDOP electrochemically prepared were dissolved in water and the solutions were then cast on glassy carbon button electrodes, followed by evaporation of water. The cyclic voltamograms of these films in organic electrolyte without monomer showed that the polymer was electroactive with a VC response quite similar to that of electrodeposited films, demonstrating that this polymer is processable and does not lose its electroactivity after dissolution and subsequent reprecipitation.

To study the optical properties of aqueous solutions of N-PrS PProDOP, polymer films were prepared on a platinum sheet working electrode from a 0.01 M monomer solution in 0.01 M LiClO4 / PC: H2O (94 : 6) using a current density of 0.04 mA / cm2 and a charge density of 0.45 C / cm2. The films were maintained at a neutralization potential (-0.7 V vs. Ag / Ag +) for 15 minutes, washed with ACN and acetone and dried in vacuo, and then dissolved in 3.0 ml of water for spectral investigations. The neutral polymer solution showed an n-n * transition at 285 nm with an absorption start of 3.45 eV. These values are shifted towards blue with respect to the values obtained for solid thin films (see table 1) as expected, since polymer chains can adopt conformations with more average torsion. Patil et.al. reported similar displacements for the poly-3 (alkane sulfonate) thiophenes.

Colorimetry The above results demonstrate that N-Me, N-PrS and N-Gly PProDOP have unique electrochemical and optical properties. As color is the most important property that should be taken into account in electrochromic applications, the authors studied the above polymers by colorimetry and express the results in the CIE 1931 Yxy and CIE 1976 L * a * b * color spaces as recommended by the "Commission Lighting International "(CIE). The colors observed for each polymer at different levels of doping are summarized in Table 2. After oxidation, the N-Me PProDOP changes from purple to blue, passing through a dark green intermediate. It should be noted that an intense purple color does not have a single wavelength located in the spectral locus of the CIE 1931 diagram, and the results of the addition of several absorptions located at different wavelengths in the visible spectrum. The color tone of this polymer in the CIE 1931 Yxy color space is shown in Figure 33A. Between -1,10 V and -0,30 V versus Fc / Fc +, the xy coordinates are almost invariable, which means that there is no visible change in the color of the polymer. When the potential is increased to +0.85 V, the dominant wavelength of the light transmitted through the material decreases as a result of the formation of charge conveyors, showing absorptions at longer wavelengths. At higher potentials, the transitions associated with the charge transporters decrease in intensity, as shown by the electrochemical spectrum, thus resulting in a lower absorption at longer wavelengths and, therefore, a decrease in the dominant wavelength. This behavior is quite typical for electrochromic polymers. The color tones of the N-Gly PProDOP and the N-PrS PProDOP, shown in Figures 33B and C, respectively, have similar characteristics. However, the xy coordinates of these polymers in the neutral state are close to the white point (x = 0.349, y = 0.378), indicating that the materials are colorless. As shown in Table 2, the N-Gly PProDOP and the N-PrS PProDOP change after oxidation from colorless to blue-gray, going through different shades, including light pink and gray. These colors are quite different from those observed in the PProDOP, which changes from orange to light blue-gray to brown.

The luminance, which is a coordinate of the Yxy color space, represents the brightness of a color as seen by the human eye. It also provides a lot of information since, with a single value, it provides information about the perceived transparency of a sample over the entire visible range of light. The% Y is different from the% T (single wavelength), since it takes into account the entire spectrum and light sensitivity of the human eye, which is not constant over the entire visible range. The changes in relative luminance (% Y) of N-Me and N-Gly PProDOP are presented in Figure 34. Again, the behavior of these polymers is different from that of PProDOP, which has a lower luminance when it is in a neutral state. that in the doped state, and also presents a minimum to intermediate potentials (the darkest state corresponding to a brown color). The N-Me PProDOP shows a slightly lower luminance in the neutral state (27%) than in the doped state (32%), but the response is relatively common. As noted above, the behavior of N-Gly PProDOP is quite exceptional for an electrochromic polymer and is confirmed by luminance measurements, which show that the polymer film has a luminance of almost 100% in the neutral state corresponding to a Colorless and completely transparent material. The luminance remains almost unchanged when the potential is increased to -0.20 V versus Fc / Fc +, then sharply decreases to approximately 55% at -0.10 V and stabilizes at this value to +0.85 V versus Fc / Fc +. The difference in behavior between the N-Gly PProDOP and the N-Me PProDOP is closely related to their relative band gaps. In fact, the transition from n to n * in the N-Gly PProDOP is completely in the UV range and not even the tail of the transition overlaps with the visible range of light. As a consequence, the decrease in the n-n * transition has no effect on the color of the polymer. Therefore, only the transitions associated with the load conveyors give rise to a visible color. The N-PrS ProDOP shows similar behavior. The ability to switch between a colorless neutral state and a blue-gray doped state gives these electrochromic materials the little frequent property of being truly anodic in color.

Conclusions In summary, a series of N-substituted PProDOPs have been prepared that show reversible and long-lasting electrochemistry, together with good electrochromic properties. The low mid-curve potentials confer a high degree of stability in the doped state, since air and moisture are not likely to reduce oxidized forms. The N-substitution allows a fine adjustment of the band gap and, therefore, of the optical properties of the resulting materials. The ability to design and synthesize polymers of pure anodic coloration has been demonstrated with N-PrS and N-Gly PProDOP. The ease with which these new compounds can be derivatized opens a wide variety of possibilities for the production of advanced polymers for screen applications, including electrochromic devices. In particular, the introduction of appropriate substituents into the propylenedioxy ring resulted in anodic, self-supporting and soluble coloration polymers, which may be of great interest for processable electrochromic materials in screen applications.

Example 8 - Gold modeling by metal vapor deposition

3,4-Ethylenedioxythiophene (EDOT), obtained commercially, was purified by column chromatography. 2,5bis (3,4-ethylenedioxythiophene) -1,4-didodecyloxybenzene (PBEDOT-B (OC12H25) 2) was synthesized according to procedures known in the art. Propylene carbonate (PC) was used without any purification. Tetrabutylammonium perchlorate (TBAP) (Aldrich Chemical Co., Inc. Milwaukee,> 99%) was used as electrolyte during electrosynthesis and polymer characterizations. For the solid state device, poly (methyl methacrylate) (PMMA) containing tetrabutylammonium trifluoromethanesulfonate was prepared according to procedures known in the art.

The fabrication of the modeled electrodes was performed using masks. The negatives were cut on a thin brass sheet of 4.5 cm x 4.5 cm, 0.25 mm as shown in Figure 35A-C. The negatives comprise 2 independent pixels (Figure 35A); 2x2 dual (figure 35B); or 3x3 (figure 35C). Porous polycarbonate membranes (Osmonics Inc., 10 μm pore size) were used as metallizable substrates. The membranes were sandwiched in a sandwich structure between the glass and the cover masks (see Figure 35D). The sandwich is attached to a rotary controller in a high vacuum chamber. Gold (99.99%) was deposited on the membrane using a thermal metal evaporation technique (Denton Vacuum, DV-502A) until the thickness reached 50 nm (to obtain good conductivity and to prevent pore sealing for the gold). The films are prepared in a potentiostatic way 1.2V (deposition of PEDOT) or by cyclic multibarring voltamograms from -0.7V to 1.3V (PBEDOT-B (OC12H25) 2). The load (Qp) was 75 mC (PEDOT) and 30 mC (bisEDOT-Phen) during the deposition procedure. Two types of counter electrodes (EC) could be used. The first was composed of a layer of anodically polymerized PEDOT on a thin sheet of gold / Mylar. The second was a second metallized membrane coated by a layer of PEDOT. Regardless of the area of the modeled electrode, the charge required for the deposition of the PEDOT is the same as the charge deposited on the working electrode.

For the electrodeposition and characterization of the polymer two cells were used in parallel. The first contained 0.05 M monomers in 0.1 M TBAP / PC equipped with a pseudo Ag reference (the potentials were calibrated using Fc / Fc +, assuming they were +0.07 V versus reference Ag / Ag +), a Pt 2X2 cm2 (EC) counter electrode and a gold metallic membrane as the working electrode. The second cell had no monomer and contained TBAP in 0.1 M PC to allow polymer characterization.

Depending on the nature of the CE, two systems, D1 and D2, can be constructed (see Figure 35F). In D1, the PEDOT CE looks towards the working electrode (ET). This contrasts with D2, where both electrodes are assembled with their backs to each other. Normally, the membrane and the EC are sandwiched in a sandwich structure between two plastic sheets and included in gel electrolyte. EDOT and PBEDOT-B (OC12H25) 2 have the same transparent character after oxidation, while, after reduction, the PEDOT appears dark blue and PBEDOT-B (OC12H25) 2 is red-purple (see figure 36).

The metallized membranes of the invention allow rapid electrolyte filtration through the membrane at the back of the polymers during the charge / discharge procedures. As a result, the authors expected a rapid color change in a solid-state device, comparable to that observed for the change using classical electrode distributions in solution. Figure 35E shows the shapes modeled on the glass substrate, the membrane and the penetration of gold through the pores. This illustrates that the metallized membrane is also porous and that ionic transport can occur in solid state devices. The penetration of gold through the pores can cause a sufficient amount of gold to remain on the inner walls of the various pores, so that the electrical contact with the gold of the upper part of the membrane can be established by making contact with the lower part of the membrane and, therefore, the gold of the inner walls of the pores. This may allow the electrical connection between the electrode pads of the upper part of the membrane to be established by making contact with the lower part of the membrane.

The authors have built a device that comprises a single PEDOT pixel as an active change surface. The PC proved to be a useful solvent to perform electrochemistry with polycarbonate membranes. The polymerization charge density is 50 mC / cm2 and the film deposits homogeneously over the entire membrane, suggesting that no surface resistance induces an ohmic drop in the electrode. After oxidation, the PEDOT layer is fully transmitting in the visible range, while it is fully absorbent in the reduced state, as expected.

The one pixel device was constructed according to the procedure of D2 (Figure 35E) using the same amount of PEDOT in the CE. Figure 37A shows the oxidized (left) and reduced (right) state of the PEDOT during the change stages. Figure 37B shows the graph of the dependence of the loading / unloading time. This device could be reversibly changed between the bleached and colored states several hundred times without loss of electroactivity as a consequence. The completion of the transition occurs in 1 second.

A 2x2 pixel device (figure 38) allowed the authors to develop electrochromic dual polymer devices. First, PEDOT was deposited on 2 pixels, using a 1.2 V potentiostatic procedure until a load of 75mC was passed. Second, PBEDOT-B (OC12H25) 2 was deposited on the other pixels using several VC scans between -0.7 and + 1.3V. This allowed uniform deposition on all pixels. The final deposition load for this stage was adjusted to 30mC to guarantee the same discolored state of the oxidized polymer, while the reduced state remains very colored in red. Figures 39A-39C provide the VC in the monomer-free solution for the PEDOT (39A), the PBEDOT-B (OC12H25) 2 (39B) and both films coupled together (39C). Figure 38 shows a photograph of the membrane coated with dual polymers in two extreme stages (discolored and colored). Figure 40 illustrates the loading of the device in solution showing the transition from discolored to colored in the interval of one second.

Example 9 - Linear modeling electrodes for electrochromic devices

Computer generated designs were printed on a smooth transparency material. Gold deposition on unprinted areas was carried out using the procedures provided in US Pat. UU. No.

3,676,213 (which is incorporated herein by reference in its entirety). The removal of printed lines / areas after the deposition of gold was carried out by sonicating the substrate in toluene.

The electrode designs used in this work are shown in Figures 35A-35C, 41 and 49A-49B, and can be printed using a laser printer on a plain transparent material. The white regions represent where the gold coating can occur. The black lines and zones (printer ink) were removed after the deposition of gold by sonication in toluene solution for 20 seconds. The surface resistivity between modeled lines was greater than 20 MO / �. Optical micrographs of interdigitated substrates at different magnifications (Figures 50A-50C) demonstrated the deposition of selected gold over regions where the ink is not present. The lateral resolution of the metallization was determined to be ~ 30 μm (Figure 50C).

Linear modeling procedures benefit from the difference in reaction of the coating material with the substrate and the lines printed on it. The commercial dispersion of PEDOT ("Baytron P", Bayer Corp.) wets plain transparency paper, but not printed lines. Multiple PEDOT coatings were applied on printed substrates (S1, S2 and S3, where the subscript indicates the number of coatings). The surface resistivities were measured as 40.9, 15.4 and 10.8 kO / � for S1, S2 and S3, respectively. Since the coating is carried out by spreading the PEDOT on the transparency film by means of a test tube, these values only give a slight idea about the increase in conductivity by increasing the number of coatings. The results suggest that the second coating (S2) has a greater effect on the increase in conductivity in relation to the third. The interdigitated designs of the electrodes coated with PEDOT (Figures 41 and 42) were prepared using a computer-aided design (CAD) computer program. Printer ink was removed by sonicating the transparency material in toluene solution. The color shown in Figure 41 is the actual color of PEDOTrPSS coated films measured by a Minolta CS-100 colorimeter. A copper tape was attached to both ends of the films to provide electrical contact. The percentage transmittance (% T) of the linearly modeled PEDOT films is of the order of 80% in the regions of the visible and the near IR in front of the air, as shown in Figure 43.

Transparent ITO-coated plastic substrates (6 cm x 4 cm) were interleaved using linear modeling (the substrates comprised nine ITO-coated conductive lines (Line width: 4 mm;), parallel to each other, separated by non-conductive gaps (Gap width: 1 mm) (for example, figures 41 and 47)). PEDOT electrodeposition on these substrates provided uniform films and different colors with strong color contrasts between the redox states (Figure 48). The white regions are non-conductive plastic regions and the blue regions are ITO coated conductive plastic.

EC films of poly (3,4-ethylenedioxythiophene) (PEDOT) (E = 1.10V vs. Ag / Ag +) were grown potentiostatically on EDOT substrates (0.01 M) in TBAP (0.1 M) / ACN. Oxidation of monomers: 0.83 V against Ag / Ag +. EC films of PBEDOT-Cz (E = 0.5 V vs. Ag / Ag +) were grown potentiostatically on BEDOT-Cz substrates in TBAP (0.1 M) / ACN. Oxidation of monomers: 0.48 V against Ag / Ag +. A platinum sheet is used as the counter electrode. All films are cleaned with electrolyte solution without monomer immediately after growth. PEDOT EC films are changed in electrolyte between -1.2 V and 1.2 V versus Ag / Ag +. The EC films of PBEDOT-Cz are changed in electrolyte between -1.2 V and 0.7 V versus Ag / Ag +.

The electrochemical deposition of the PEDOT of cathode coloration, electrochromic (EC), on linearly modeled substrates provided homogeneous films with very little IR drop. The electrochromic change of the PEDOT between its redox states was achieved by increasing the potential between -1.2 V (neutral, colored) and + 1.2 V (doped, transmitter) versus Ag / Ag + (Figure 44A). The PEDOT EC is deposited on all other lines as a result of linear modeling. The optical micrograph of the film showed that there are no short circuits between the lines (Figure 44B). The black spots on the micrograph are due to residual toner inks of the laser pointer. They are not the result of electrodeposition because they also exist in isolated sites, without deposits.

In order to determine the electrochemical stability of the films, chronoculombimetry experiments (load monitoring over time) were carried out increasing the potential between -1.2 V (25 s) and 1.2 V (25 s) against Ag / Ag +. The doping / doping load was found to be ~ ± 1.5 mC / cm2 with a maximum doping current of ~ ± 0.12 mA / cm2 (imáx). The first 25 square waves did not result in the reduction of the image. After 200 square waves, the image fell to 0.08 mA / cm2.

PBEDOT-Cz, a multi-colored, anodic, electrochromic colored polymer, is considered the complementary polymer for the PEDOT EC of cathodic coloration. It changes between pale yellow (reduced) and blue (fully oxidized) with an intermediate green color. Figure 46 illustrates the color change of a PBEDOT-Cz film between its redox states in a three electrode electrochemical cell. Quantitative color measurement was carried out using a colorimeter. Figure 45 shows the color change of the PBEDOT-Cz on Baytron P linearly modeled electrode to various potentials based on the values of L * a * b recorded by the colorimeter. Since the measurement zone of the colorimeter is larger than the target area of the substrate, the color measured by the colorimeter does not match exactly the color of the photograph (that is, the mixing of neighboring color lines occurs). The electrochromic change of PBEDOT-Cz in TBAP is illustrated in Figure 46.

Highly conductive metal modeled electrodes (for example, gold) are useful for the deposition of high quality conductive polymer films and rapid EC change. Vapor deposition techniques require high deposition temperatures (> 400 ° C) and very low pressures, which impose limitations for substrate materials.

5 Gold linear modeling substrates were used to construct lateral EC devices. The PEDOT was used as the active EC material and was electrochemically deposited on the lines from its monomer solution. Polymer deposition occurred in all other lines as a result of linear modeling. A solid state device was mounted by depositing PEDOT on each set of EID fingers separately. Gel electrolyte was applied on the substrate to provide ionic conductivity between electrically insulated lines. Be

10 observed an EC change between intense blue and golden reflector states (figure 51). The complete discoloration / coloration occurred in less than 3 seconds.

In another example, a dual modeled gold electrode was used to determine the effect of the electrode design on the change characteristics (Figure 52). To achieve this, the PEDOT EC was deposited separately on both sides at equal deposition loads. The left rectangle was set as the anode and the right rectangle was set as the anode

15 cathode (two electrode cell configuration). The change of this device was carried out in a liquid electrolyte applying ± 0.5 volts (figure 52). The change between redox states was less than 3 seconds. The solid state assembly of this device, using the gel electrolyte as the ion conducting medium, increased the change time. The voltage required to change the device was also increased to ± 1.5 V due to the high IR drop of the solution between rectangles (Figure 53).

20 Example 10 - Vulcanization with ITO

ITO / glass substrate modeling is possible by vulcanization procedures. These procedures require burning ITO through a metal tip in a closed circuit using a power supply. The profilometric analysis of the vulcanized lines showed the total elimination of the ITO from the lines drawn by the metal tip. Figure 54A shows an optical micrograph of a vulcanized line on a substrate of

25 ITO / glass. The lateral resolution of the lines was determined to be 60 μm. Figure 54B shows a profile scan of a vulcanized line. The lines drawn on ITO / glass by this procedure resulted in the isolation of regions modeled by> 20 MO.

ITO removal from plastic substrates can be accomplished simply by scratching the plastic substrate with a metal blade using a plastic ruler. A modeling was designed that included the letters U and F with

30 the Microsoft Word 2000 Paint software and this modeling was drawn on ITO coated polyester using a metal tip (Figure 55A). This procedure mechanically removed the ITO from the plastic surface. The modeled ITO substrate was then treated with a 2M HCl solution to remove all residues.

The scraped ITO / plastic electrode was then used for electrochemical deposition of poly (3-methylthiophene) (P3MTh). P3MTh is an electrochromic polymer, which reversibly changes between its red-orange states

35 (neutral) and blue (oxidized). The P3MTh was deposited on the letters U and F separately. A lateral electrochromic device was constructed by assigning the letter U as the anode and the letter F as the cathode. The electrochromic change of this device in liquid electrolyte is shown in Figure 55B.

The file of this patent contains at least one drawing made in color. The US Patent and Trademark Office. UU. will provide copies of this patent with color drawings upon request and payment of the necessary fees.

Table 1:

Polymer

Eox / mon (V) vs. Fc / Fc + E1 / 2 versus Fc / Fc + (V) ipa / ipc * .Ep * (mV) Amáx (nm) Eg (eV)

PProDOP

+0.58 -0.89 1.39 160 482/523 2.2

N-Me PProDOP

+0.50 -0.24 1.35 92 330 3.0

N-Pr PProDOP

+0.51 -0.16 1.02 8 306 3.4

N-Oct PProDOP

+0.52 -0.14 1.02 6 - -

N-Gly PProDOP

+0.54 -0.13 0.99 2 306 3.4

* Scanning speed: 20 mV / s LV / S

Table 2:

Polymer

E (V) vs. Fc / Fc + Y % L to b Color

N-Me PProDOP

-1.10 25.9 58 eleven 0 deep purple

-0.30

27.1 59 10 2

-0.15

28.7 60 4 8

0.00

30.1 62 -one 5 dark green

+0.10

30.8 62 -3 3

+0.20

31.3 63 -3 0 blue

+0.50

32.2 64 -4 -3

+0.70

31.7 63 -5 -4

N-Gly PProDOP

-0.60 99.6 98 0 4 colorless

-0.20

98.6 97 0 4

-0.10

90.2 94 2 4 light pink

0.00

61.3 81 one 12 grey rose

+0.20

58.9 79 -3 7 Gray

+0.30

58.9 79 -4 5

+0.40

58.9 79 -5 3

+0.50

58.9 79 -6 one blue gray

+0.70

58.5 79 -6 -one

Table 3: SPECIFIC ELECTROCROMIC POLYMERS

Acronyms

Properties Chemical names

PEDOT

one poly (3,4-ethylenedioxythiophene)

PProDOT

one poly (3,4-propylenedioxythiophene)

PProDOT-Me2

one poly (3,4- (2,2-dimethylpropylene) dioxythiophene)

PEDOP

one poly (3,4-ethylenedioxypyrrole)

PProDOP

one poly (3,4-propylenedioxypyrrole)

PProDOP-NPS

one poly (N- (3-sulfonatopropoxy) -3,4-propylenedioxypyrrole)

PBEDOT-V

one poly (1,2-bis (2-ethylenedioxythienyl) vinyl)

PProDOT-V

one poly (1,2-bis (2-propylenedioxythienyl) vinyl)

PBEDOT-Pyr

1.2 poly (2,5-bis (2-ethylenedioxythienyl) pyridine)

PBEDOTB (OC12H25) 2

one poly (1,4-bis (2-ethylenedioxythienyl) -2,5-didodecyloxybenzene)

P3MTh

one poly (3-methylthiophene)

PBEDOT-Fu

one poly (2,5- (2-ethylenedioxythienyl) furan)

PBEDOT-BP

one poly (4,4 '- (2-ethylenedioxythienyl) biphenyl)

PBEDOT-Cz

one poly (3,6- (2-ethylenedioxythienyl) carbazole)

P3BTh

one poly (3-butylthiophene)

1-dopable compound of type p 2-dopable compound of type n

Table 4: GENERAL ELECTROCROMIC POLYMERS

Acronyms

Properties Chemical names

PTh

one polythiophene

Pfu

one polyfuran

Ppy

one polypyrrole

PPV

1.2 poly (1,4-phenylene vinyl)

MEH-PPV

one 2-Methoxy-5-ethylhexyloxy poly (1,4-phenylene vinyl)

PCz

one polycarbazole

alkyl-PEDOT

one alkylpoli (3,4-ethylenedioxythiophene)

aril-PEDOT

one aryl poly (3,4-ethylenedioxythiophene)

PSNS

one poly (2,5- (2-thienyl) pyrrole)

PV

one polyvinogen

PMPhth

one poly (metal phthalocyanines)

PBiEDOT

one poly (5,5'-byethylenedioxythiophene)

PBEDOT-CNV

one poly (1,2- (2-ethylenedioxythienyl) cyanovinylene)

PBTh-CNV

one poly (1,2- (2-thienyl) cyanovinylene)

PBEDOT-PyrPyr (Ph) 2

1,2,3 poly [2,5-bis (2-ethylenedioxythienyl) -diphenylpyrididopyrazine]

1-dopable compounds of type p 2-dopable compounds of type n 3-has four (4) color states

Table 5: Exemplary complementary electrochromic polymers

Kind

Movie State 1 State 2

one

one

T < CI

one

2 T < C2

2

one C1 < C2

2

2

C1 < C3

3

one C1 < C2

3

2 C3 < C4

4

one T < CI

4

2 T < CI

5

one C1 < C2

5

2 C1 < C2

Table 6: Complementary EC polymers and exemplary colors

Electrodes "same polarization"

Kind

State 1 State 2

+

-

one

T < blue PEDOT

one

T < Red PBEDOT-B (OC12H25) 2

one

T < blue PEDOT

one

T < orange PProDOP

one

T < blue PEDOT

one

T < Red PEDOP

+

< -

2

blue < Red P3MTh

2

Gray < orange PProDOP

2

blue < yellow PBEDOT-Cz

2

blue < Red P3MTh

2

blue < yellow PBEDOT-Cz

2

blue < Red PBEDOT-B (OC12H25) 2

2

blue < yellow PBEDOT-Cz

2

blue < Red PBEDOT-Fu

Table 7: Complementary EC polymers and exemplary colors

Electrodes "opposite polarization"

Kind

+ / - / +

3

T < blue PEDOT

3

Yellow t < blue PBEDOT-Cz

3

blue < Yellow t PBEDOT-Cz

3

Red < Blue t PBEDOT-B (OC12H25) 2

3

Red < blue P3MTh

3

Orange < Gray PProDOP

3

T < blue PEDOT

3

Red < blue P3BT

Table 8: General modeling procedures

Modeling procedure

Resolution Short description

Photolithographic techniques

~ 1 μm; limited by light diffraction Direct photon-dependent writing techniques (for example, laser ablation). Complicated and expensive.

Microcontact printing (μCP)

edge roughness ~ 1-2 μm. Monolayers modeling using a seal that allows the polymerization of the selected area.

Scanning probe microscopy

~ 3 μm An MSB (ultra-micro electrode) tip writes polymer lines on the substrate.

Inkjet printing

Limited by printer resolution (5-100 μm) Commercial inkjet printers can be used to print soluble polymers.

Serigraphy

~ 10 μm Requires processable (soluble) polymers.

Line modeling

2-30 μm Use the difference in reaction with the substrate and the lines printed on it.

one.

J. Kido, M. Kimura, K. Nagai, Science 267, 1332 (1995)

2.

I. D. Brotherston, D. S. K. Mudigonda, J. M. Osbron, J. Belk, J. Chen, D. C. Loveday, J. L. Boehme, J. P. Ferraris, D. L. Meeker, Electrochim. Minutes 44, 2993 (1999)

3.

I. Schwendeman, J. Hwang, D. M. Welsh, D. B. Tanner, J. R. Reynolds, Adv. Mater. 13, 634 (2001)

Four.

D. R. Rosseinsky, R. J. Mortimer, Adv. Mater. 13, 783 (2001)

5.

R. D. Rauh, Electrochim. Minutes 44, 3165 (1999)

6.

C. Arbizzani, M. Mastragostino, A. Zanelli, Solar Energy Materials and Solar Cells 39, 213 (1995)

7.

C. L. Lampert, Solar Energy Materials and Solar Cells 52,207 (1998)

8.

J. Kim, T. M. Swager, Nature 411,1030 (2001)

9.

H. Sirringhaus, N. Tessler, R. H. Friend, Science 280.1741 (1998)

10.

A. Montali, C. Bastiaansen, P. Smith, C. Weder, Nature 392, 261 (1998)

eleven.

M. Granstrom, K. Petritsch, A. C. Arias, A. Lux, M. R. Andersson, R. H. Friend, Nature 395, 257 (1998)

12.

B. C. Thompson, P. Schottland, K. Zong, J. R. Reynolds, Chem. Mater. 12, 1563 (2000)

13.

L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J. R. Reynolds, Adv. Mater. 12, 481 (2000)

14.

P. L. Burn, A. B. Holmes, A. Kraft, D. D. C. Bradley, A. R. Brown, R. H. Friend, R. W. Gymer, Nature 356, 47 (1992)

fifteen.

W. A. Gazotti, G. Casalbore-Miceli, A. Geri, A. Berlin, M. A. De Paoli, Adv. Mater. 10.1522 (1998)

16.

O. Inganas, T. Johansson, S. Ghosh, Electrochim. Minutes 46, 2031 (2001)

17.

G. A. Sotzing, J. R. Reynolds, P. J. Steel, Adv. Mater. 9, 795, (1997)

18.

S. A. Sapp, G. A. Sotzing, J. R. Reynolds, Chem. Mater. 10, 2101 (1998)

19.

S. A. Sapp, G. A. Sotzing, J. L. Reddinger, J. R. Reynolds, Adv. Mater. 8, 808 (1996)

twenty.

R. D. Rauh, F. Wang, J. R. Reynolds, D. L. Meeker, Electrochim. Minutes 46, 2023 (2001)

twenty-one.

Deb, S. K. Appl. Opt. Suppl. 1969, 3, 192.

22

Monk, P. M. S .; Mortimer, R. J .; Rosseinsky, D. R. Electrochromism: Fundamentals and Applications; VCH, Weinheim, 1995.

2. 3.

Granqvist, C. G .; Azens, A .; Isidorsson, J .; Kharrazi, M .; Kullman, L .; Lindstroem, T .; Niklasson, G. A .; Ribbing, C.-G .; Roennow, D .; Stromme Mattsson, M .; Veszelei, M. J. Non-Cryst. Solids 1997,218, 273.

24.

Monk, P. M. S. J. Electroanal. Chem. 1997, 432,175.

25.

Bange, K. Solar Energy Mat. Solar Cells 1999, 58, 1.

26.

Granqvist, C. G .; Azens, A .; Hjelm, A .; Kullman, L .; Niklasson, G. A .; Ribbing, C-G .; Roennow, D .; Stromme Mattsson, M .; Veszelei, M .; G. Vaivars Solar Energy 1998, 63, 199.

27.

Agnihotry, S. A .; Pradeep; Sekhon, S. S. Electrochemica Acta 1999, 44, 3121.

28.

Rauh, R. D. Electrochemica Acta 1999, 44, 3165.

29.

Tracy, C. E .; Zhang, J.-G .; Benson, D. K .; Czanderna, A. W .; Deb, S. K. Electrochemica Acta 1999, 44, 3195.

30

Pennisi, A .; Simone, F .; Barletta, G .; Say Marco, G .; Lanza, L. Electrochemica Acta 1999, 44, 3237.

31.

Meeker, D.L .; Mudigonda, D.S.K .; Osborn, J.M .; Loveday, D.C .; Ferraris, J.P. Macromolecules 1998, 31,2943.

32

Mudigonda, D.S.K .; Meeker, D.L .; Loveday, D.C .; Osborn, J.M .; Ferraris, J.P. Polymer 1999, 40, 3407.

33.

Brotherson, I.D .; Mudigonda, D.S.K .; Ocborn, J.M .; Belk, J .; Chen, J .; Loveday, D.C .; Boehme, J.L .; Ferraris,

J.P .; Meeker, D.L. Electrochimica Acta, 1999,44, 2993.

3. 4.

Byker, H. J. Gentex Corporation, US Pat. UU. No. 4902108.

35

Mortimer, R. G. Chem. Soc. Rev. 1997,26,147.

36.

Dautremont-Smith, W. C. Displays 11982, 3.

37.

Mortimer, R. J. Electrochimica Acta 1999, 44, 2971.

38.

De Paoli, M.-A .; Casabollore-Miceli, G .; Girotto, E. M .; Gazotti, W. A. Electrochimica Acta 1999, 44,2983.

39.

Mastrogostino, M. Applications of Electroactive Polymers, Scrosati, B., ed .; Chapman and Hall: London, 1993.

40

Sapp, S. A .; Sotzing, G. A .; Reynolds, J. R. Chem. Mater. 1998,10, 2101.

41.

Kumar, A .; Welsh, D. M .; Morvant, M. C; Piroux, F .; Abboud, K. A .; Reynolds, J. R. Chem. Mater. 1998,10, 896.

42

Skotheim, T.A .; Elsenbaumer, R.L .; Reynolds, J.R. Handbook of Conducting Polymers, 2nd ed .; Marcel Dekker: New York, 1998

43

Nalwa, H.S. Handbook of Organic Conductive Molecules and Polymers; John Wiley and Sons: New York,

1997

44.

G. A. Sotzing, J. R. Reynolds, J. Chem. Soc, Chem. Commun., 703 (1995)

Four. Five.

G. A. Sotzing, C. A. Thomas, J. R. Reynolds, P. J. Steel, Macromol. 31, 3750 (1998)

46.

46 Gritzner, G .; Kuta, G. J. Pure Appl. Chem. 1984,56, 461.

47

Zong, K .; Reynolds, J. R. J. Org. Chem., 2000, submitted.

48.

Overheim, R. D .; Wagner, D. L. Light and Color, Wiley: New York, 1982, p.77.

49.

Zotti, G .; Schiavon, G .; Berlin, A .; Pagani, G. Chem. Mater. 1993, 5,430.

fifty.

Waltman, R.J., Bargon, J. Can. J. Chem., 1986, 64,16.

51.

Zotti, G .; Martina, S .; Wegner, G .; Schlttter, A. D. Adv. Mater. 1992, 4,798.

52

Diaz, A. F .; Castello, J .; Logan, J. A .; Lee, W. Y. J. Electroanal. Chem. 1981,129, 115.

53.

Diaz, A. F .; Bargon, J. Handbook of Conducting Polymers, 1st ed., Vol. I, ed. Skotheim, T. J .; Marcel Dekker: New York; 1986, p.81.

54

Doblhofer, K .; Rajeshwar, K. Handbook of Conducting Polymers, 2nd ed., Eds. Skotheim, T. J .; Elsenbaumer, R. L .; Reynolds, J. R .; Marcel Dekker: New York; 1998, p.531.

55.

Thompson, B. C; Schottland, P .; Zong, K .; Reynolds, J. R. Chem. Mater. 2000, presented.

56.

CIE; Colorimetry (Official Recommendations of the International Lighting Commission), CIE Publi. No. 15, Paris, 1971.

57.

Wyszecki, G .; Stiles, W. S. Color Science; Wiley: New York, 1982.

58.

Nassau, K. Color for Science, Art and Technology, Elsevier: Amsterdam, 1998.

59.

Gritzner, G .; Kuta, G. J. PureAppl. Chem. 1984, 56, 461.

Claims (18)

one.

An electrochromic polymer, comprising:

an anodic coloring polymer comprising a substituted N-alkyl poly (3,4-propylenedioxypyrrole), in which the coloring polymer provides a band gap (Eg) � 3.0 eV and has an oxidation potential of less than 0.5 V versus a saturated Calomelan electrode (ECS).

2.

The electrochromic polymer of claim 1, wherein the substituted N-alkyl poly (3,4-propylenedioxypyrrole) is N-Me PProDOP, N-Pr PProDOP, N-Oct PProDOP, N-Gly PProDOP, N-PrS PProDOP or PProDOP-BuOH.

3.

The electrochromic polymer of claim 1, wherein the polymer has an oxidation potential in the range between -0.2 and -0.0 volts compared to a saturated calomelan electrode (ECS).

Four.

The electrochromic polymer of claim 1, wherein the polymer has an oxidation potential of less than 0.0 volts against a saturated calomelan electrode (ECS).

5.

The electrochromic polymer of claim 1, wherein the polymer has an oxidation potential of less than 0.2 volts versus a saturated calomelan electrode (ECS).

6.

The electrochromic polymer of claim 1, wherein the polymer has an oxidation potential of less than 0.4 volts versus a saturated calomelan electrode (ECS).

7.

An electrochromic device, comprising: a first electrode; a second electrode; an anodic coloring polymer in contact with the second electrode; a cathodic coloration polymer in contact with the first electrode; and an electrolyte located between and in contact with the anodic coloring polymer and the coloring polymer

cathodic, characterized in that the anodic coloring polymer comprises an N-alkyl substituted poly (3,4-propylenedioxypyrrole), provides a band gap (Eg) � 3.0 eV and has an oxidation potential of less than 0.5 V in front of a saturated Calomelan electrode (ECS), and in which the device is optically transparent when a positive voltage is applied to the first electrode with respect to the second electrode and colored after the application of a negative voltage to the first electrode with respect to the second electrode .

8.

The electrochromic device of claim 7, wherein the substituted N-alkyl poly (3,4-propylenedioxypyrrole) comprises N-Me PProDOP, N-Pr PProDOP, N-Oct PProDOP, N-Gly PProDOP, N-PrS PProDOP or PProDOP-BuOH.

9.

The electrochromic device of claim 7, wherein the cathodic coloring polymer is poly (3,4-alkylenedioxythiophene).

10.

The electrochromic device of claim 9, wherein the poly (3,4-alkylenedioxythiophene) is PEDOT, PProDOT or PProDOT-Me2.

eleven.

The electrochromic device of claim 9, wherein the cathodic coloring polymer is a poly (3,4-propylenedioxythiophene).

12.

The electrochromic device of claim 11, wherein the poly (3,4-propylenedioxythiophene) is PProDOT-Me2.

13.

The electrochromic device of claim 7, wherein the cathodic coloring polymer is PBEDOT-V, PProDOT-V, PEDOP or PProDOP.

14.

The electrochromic device of claim 7, wherein the anodic coloring polymer has an oxidation potential in the range between -0.2 and -0.0 volts versus a saturated calomelan electrode (ECS).

fifteen.

The electrochromic device of claim 7, wherein the anodic coloring polymer has an oxidation potential of less than 0.0 volts against a saturated calomelan electrode (ECS).

16.

The electrochromic device of claim 7, wherein the anodic coloring polymer has an oxidation potential of less than 0.2 volts against a saturated calomelan electrode (ECS).

17.

The electrochromic device of claim 7, wherein the anodic coloring polymer has an oxidation potential of less than 0.4 volts compared to a saturated calomelan electrode (ECS).

18.

The electrochromic device of claim 7, wherein the device switches between an optically transparent state and a colored state in less than one second.